Acid dyes, process for the production thereof and their use

ABSTRACT

Dyes of formula (1) 
                         
their production and their use are described.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371) of PCT/EP2014/072634, filed Oct. 22, 2014, which claims benefit of European Application No. 13190664.6, filed Oct. 29, 2013, both of which are incorporated herein by reference in their entirety.

The present invention relates to the technical field of dyestuffs for dyeing and printing of hydroxyl- and/or carboxamido-containing material.

Acid dyes containing pyridine derivatives as couplers are known from prior art and can be used as colorants in different applications, see for example GB 2 337 053 A, which discloses dyes as part of ink jet formulations, which bisazo-dyes are based on hydroxypyridone and pyridinium as structural elements. According to the examples the dyes disclosed are used as neutral molecules for printing paper. Other dyes are disclosed in e.g. U.S. Pat. No. 3,959,250 A, U.S. Pat. No. 5,468,848 A, U.S. Pat. No. 3,960,480 A, U.S. Pat. No. 5,543,259 A and WO 2007/045825 A.

However, in the context of the dyeing and printing of hydroxyl- and/or carboxamido-containing material the known dyes have a number of technical disadvantages, which require improvement.

One such disadvantage is, that many of them are comprising heavy metals such as Cu, Cr or Ni. Such heavy metals are critical from a toxicological as well as an environmental point of view and shall thus be excluded.

Surprisingly, it has now been found that the dyes of the formula (1) as described below show highly advantageous properties over the known dyes. These include high tinctorial strength with high brilliancy as well as high fastness properties such as wash, contact and light fastness on the materials mentioned above, on blends containing them as well as on microfibres. Most importantly, dyes of formula (1) are substantially heavy metal free and provide dyeings that are levelled. Metals may only be present as counter ions and are selected from the groups of alkali and earth alkali metals, which do not have such effects as heavy metals.

If heavy metals are present at all in the dyes of the present invention they do not result from being integral part of the dye but are coursed by the production process in general. Reasons in general for these impurities can be impurities resulting from educts and catalysts being used in the respective reactions—the levels of such impurities can be managed and be kept well below those recommended e.g. by ETAD® and would thus be below 100 ppm for Cr, below 250 ppm for Cu and below 200 ppm for Ni just to mention the values for the metals mentioned above. This is a significant improvement as compared to dyes where such metals are present at molar levels.

The present invention refers to dyes of formula (1)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M whereby at least two of them are SO₃M, R⁹ and R¹⁸ independent of each other is cyano, carbamoyl, substituted carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen, R¹⁰ and R¹⁹ independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl-amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido, R¹¹, R¹², R²⁰ and R²¹ independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamo-yl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M, R¹³, R¹⁴, R¹⁵, R¹⁶, R²², R²³, R²⁴ and R²⁵ independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo-alkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkyl-sulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M, R¹⁷ and R²⁶ independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M, M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation, m, n, o and p independent of each other is integer 1, 2, 3 or 4, when n is 2, 3 or 4, R¹³ contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R¹⁴ independently from R¹³, when m is 2, 3 or 4, R¹⁵ contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R¹⁶ independently from R¹⁵, when o is 2, 3 or 4, R²² contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R²³ independently from R²² and when p is 2, 3 or 4, R²⁴ contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R²⁵ independently from R²⁴, the dyes of formula (1) have two to six sulfonic acid groups and whereby the bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R¹¹ and R¹², and R¹³ to R¹⁷, respectively can be positioned ortho or para to R⁹, meaning that when the amino rest bearing the substituents R¹¹ and R¹² is positioned ortho to R⁹, the amino rest bearing the substituents R¹³ to R¹⁷ is positioned para to R⁹, and vice versa and the same applies to the amino rests bearing the substituents R²⁰ and R²¹, and R²² to R²⁶, respectively that can be positioned ortho or para to R¹⁸, meaning that when the amino rest bearing the substituents R²⁰ and R²¹ is positioned ortho to R¹⁸, the amino rest bearing the substituents R²² to R²⁶ is positioned para to R¹⁸, and vice versa.

The present invention refers to all tautomeric and geometric isomers of the dyes of formula (1) as well as mixtures thereof.

Alkyl groups appearing in this invention may be straight-chain or branched and are (C₁-C₁₂)-alkyl groups, preferably (C₁-C₈)-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.

The same applies to alkoxy groups which accordingly are preferably (C₁-C₈)-alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably (C₁-C₈)-thioalkoxy, for example —SCH₃ or —SC₂H₅.

Cycloalkyl groups are preferably (C₃-C₈)-cycloalkyl and especially preferably cyclopentyl and cyclohexyl. The term cyloalkyl comprises for the purpose of the present invention substituted cycloalklyl groups and unsatured cycloalkyl groups as well. A preferred group of this type is cyclopentenyl. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Alkenyl groups may be straight-chain or branched and are preferably (C₂-C₆)-groups for example vinyl and allyl. The term alkenyl comprises for the purpose of the present invention alkynyl groups as well, for example ethynyl and propargyl.

Aryl groups appearing in the context of this invention are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl respectively. Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl or acyloxy.

Heteroaryl groups appearing in this invention are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1,2,4-thiadiazole, 1,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1,3,4-thiadiazole, furane, oxazole, benzoxazole or isoxazole. The terms heteroaryl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl or acyloxy.

Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine. The terms heterocycloalkyl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, amino-carbonylamino, aminosulfonylamino, alkoxycarbonyl or acyloxy.

Halogen is preferably chlorine, bromine or fluorine.

M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri- or tetra-(C₁-C₄)-alkylammonium.

Preferred are dyes of formula (1a)

wherein R^(1a), R^(2a), R^(3a), R^(4a), R^(5a), R^(6a), R^(7a) and R^(8a) independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(9a) and R^(18a) independent of each other is cyano, carbamoyl or alkoxycarbonyl, R^(10a) and R^(19a) independent of each other is unsubstituted, linear or branched (C₁-C₄)-alkyl, unsubstituted (C₅-C₇)-cycloalkyl, substituted (C₅-C₇)-cycloalkyl with one or more substituents, preferably selected from the group consisting of methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl, R^(11a), R^(12a), R^(20a) and R^(21a) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, R^(13a), R^(14a), R^(15a), R^(16a), R^(22a), R^(23a), R^(24a) and R^(25a) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, R^(17a) and R^(26a) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation, m, n, o and p independent of each other is integer and is 1, 2, 3 or 4, when n is 2, 3 or 4, R^(13a) contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R^(14a) independently from R^(13a), when m is 2, 3 or 4, R^(15a) contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R^(16a) independently from R^(15a), when o is 2, 3 or 4, R^(22a) contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R^(23a) independently from R^(22a) and when p is 2, 3 or 4, R^(24a) contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R^(25a) independently from R^(24a).

Particular preferred are dyes of formula (1aa)

wherein R^(1aa), R^(2aa), R^(3aa), R^(4aa), R^(5aa), R^(6aa), R^(7aa) and R^(8aa) independent of each other is SO₃M, hydrogen, alkyl or alkoxy whereby at least two of them are SO₃M, R^(9aa) and R^(18aa) independent of each other is cyano or carbamoyl, R^(10aa) and R^(19aa) is methyl, m, n, o and p, independent of each other is an integer and is 2, 3 or 4, R^(11aa), R^(13aa), R^(14aa), R^(15aa), R^(16aa), R^(17aa), R^(20aa), R^(22aa), R^(23aa), R^(24aa), R^(25aa) and R^(26aa) is hydrogen, R^(12aa) and R^(21aa) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylproyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-methoxyethyl, 3-methoxypropyl, 2-hydroxyethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 2-(2-hydroxyethylsulfanyl)-ethyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(ethyl-sulfonyl)ethanol, 3-(4-hydroxybutoxy)propyl, 2-(2-hydroxyethoxy)ethyl, 4-(2-hydroxyethane-sulfonyl)phenyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl and M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of preferred dyes of the formula (1aa) are the compounds of the formulae (1aa¹ to 1aa⁸¹⁶) and mixtures thereof, wherein R^(2aa) and R^(7aa) is hydrogen:

Structure R^(1aa) R^(3aa) R^(4aa) R^(5aa) R^(6aa) R^(8aa) R^(9aa)/R^(18aa) R^(12aa)/R^(21aa) m n o p 1aa¹ H SO₃H H H SO₃H H CN H 2 2 2 2 1aa² H H SO₃H SO₃H H H 1aa³ Methyl H SO₃H SO₃H H Methyl 1aa⁴ OMe H SO₃H SO₃H H OMe 1aa⁵ H SO₃H H H SO₃H H CN Ethyl 2 2 2 2 1aa⁶ H H SO₃H SO₃H H H 1aa⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁸ OMe H SO₃H SO₃H H OMe 1aa⁹ H SO₃H H H SO₃H H CN Propyl 2 2 2 2 1aa¹⁰ H H SO₃H SO₃H H H 1aa¹¹ Methyl H SO₃H SO₃H H Methyl 1aa¹² OMe H SO₃H SO₃H H OMe 1aa¹³ H SO₃H H H SO₃H H CN Butyl 2 2 2 2 1aa¹⁴ H H SO₃H SO₃H H H 1aa¹⁵ Methyl H SO₃H SO₃H H Methyl 1aa¹⁶ OMe H SO₃H SO₃H H OMe 1aa¹⁷ H SO₃H H H SO₃H H CN Pentyl 2 2 2 2 1aa¹⁸ H H SO₃H SO₃H H H 1aa¹⁹ Methyl H SO₃H SO₃H H Methyl 1aa²⁰ OMe H SO₃H SO₃H H OMe 1aa²¹ H SO₃H H H SO₃H H CN Cyclobutyl 2 2 2 2 1aa²² H H SO₃H SO₃H H H 1aa²³ Methyl H SO₃H SO₃H H Methyl 1aa²⁴ OMe H SO₃H SO₃H H OMe 1aa²⁵ H SO₃H H H SO₃H H CN Cyclopentyl 2 2 2 2 1aa²⁶ H H SO₃H SO₃H H H 1aa²⁷ Methyl H SO₃H SO₃H H Methyl 1aa²⁸ OMe H SO₃H SO₃H H OMe 1aa²⁹ H SO₃H H H SO₃H H CN Isopropyl 2 2 2 2 1aa³⁰ H H SO₃H SO₃H H H 1aa³¹ Methyl H SO₃H SO₃H H Methyl 1aa³² OMe H SO₃H SO₃H H OMe 1aa³³ H SO₃H H H SO₃H H CN Sec-butyl 2 2 2 2 1aa³⁴ H H SO₃H SO₃H H H 1aa³⁵ Methyl H SO₃H SO₃H H Methyl 1aa³⁶ OMe H SO₃H SO₃H H OMe 1aa³⁷ H SO₃H H H SO₃H H CN 2-Methyl 2 2 2 2 1aa³⁸ H H SO₃H SO₃H H H butyl 1aa³⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁰ OMe H SO₃H SO₃H H OMe 1aa⁴¹ H SO₃H H H SO₃H H CN 1-Ethyl 2 2 2 2 1aa⁴² H H SO₃H SO₃H H H propyl 1aa⁴³ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁴ OMe H SO₃H SO₃H H OMe 1aa⁴⁵ H SO₃H H H SO₃H H CN 1,2-Dimethyl 2 2 2 2 1aa⁴⁶ H H SO₃H SO₃H H H propyl 1aa⁴⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁸ OMe H SO₃H SO₃H H OMe 1aa⁴⁹ H SO₃H H H SO₃H H CN Tert-butyl 2 2 2 2 1aa⁵⁰ H H SO₃H SO₃H H H 1aa⁵¹ Methyl H SO₃H SO₃H H Methyl 1aa⁵² OMe H SO₃H SO₃H H OMe 1aa⁵³ H SO₃H H H SO₃H H CN 3-Methyl 2 2 2 2 1aa⁵⁴ H H SO₃H SO₃H H H butyl 1aa⁵⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁶ OMe H SO₃H SO₃H H OMe 1aa⁵⁷ H SO₃H H H SO₃H H CN Pentan-2-yl 2 2 2 2 1aa⁵⁸ H H SO₃H SO₃H H H 1aa⁵⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁰ OMe H SO₃H SO₃H H OMe 1aa⁶¹ H SO₃H H H SO₃H H CN 2-Ethylhexyl 2 2 2 2 1aa⁶² H H SO₃H SO₃H H H 1aa⁶³ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁴ OMe H SO₃H SO₃H H OMe 1aa⁶⁵ H SO₃H H H SO₃H H CN 2,2-Dimethyl 2 2 2 2 1aa⁶⁶ H H SO₃H SO₃H H H propyl 1aa⁶⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁸ OMe H SO₃H SO₃H H OMe 1aa⁶⁹ H SO₃H H H SO₃H H CN Phenyl 2 2 2 2 1aa⁷⁰ H H SO₃H SO₃H H H 1aa⁷¹ Methyl H SO₃H SO₃H H Methyl 1aa⁷² OMe H SO₃H SO₃H H OMe 1aa⁷³ H SO₃H H H SO₃H H CN Benzyl 2 2 2 2 1aa⁷⁴ H H SO₃H SO₃H H H 1aa⁷⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁶ OMe H SO₃H SO₃H H OMe 1aa⁷⁷ H SO₃H H H SO₃H H CONH₂ H 2 2 2 2 1aa⁷⁸ H H SO₃H SO₃H H H 1aa⁷⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁸⁰ OMe H SO₃H SO₃H H OMe 1aa⁸¹ H SO₃H H H SO₃H H CONH₂ Ethyl 2 2 2 2 1aa⁸² H H SO₃H SO₃H H H 1aa⁸³ Methyl H SO₃H SO₃H H Methyl 1aa⁸⁴ OMe H SO₃H SO₃H H OMe 1aa⁸⁵ H SO₃H H H SO₃H H CONH₂ Propyl 2 2 2 2 1aa⁸⁶ H H SO₃H SO₃H H H 1aa⁸⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁸⁸ OMe H SO₃H SO₃H H OMe 1aa⁸⁹ H SO₃H H H SO₃H H CONH₂ Butyl 2 2 2 2 1aa⁹⁰ H H SO₃H SO₃H H H 1aa⁹¹ Methyl H SO₃H SO₃H H Methyl 1aa⁹² OMe H SO₃H SO₃H H OMe 1aa⁹³ H SO₃H H H SO₃H H CONH₂ Pentyl 2 2 2 2 1aa⁹⁴ H H SO₃H SO₃H H H 1aa⁹⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁹⁶ OMe H SO₃H SO₃H H OMe 1aa⁹⁷ H SO₃H H H SO₃H H CONH₂ Cyclobutyl 2 2 2 2 1aa⁹⁸ H H SO₃H SO₃H H H 1aa⁹⁹ Methyl H SO₃H SO₃H H Methyl 1aa¹⁰⁰ OMe H SO₃H SO₃H H OMe 1aa¹⁰¹ H SO₃H H H SO₃H H CONH₂ Cyclopentyl 2 2 2 2 1aa¹⁰² H H SO₃H SO₃H H H 1aa¹⁰³ Methyl H SO₃H SO₃H H Methyl 1aa¹⁰⁴ OMe H SO₃H SO₃H H OMe 1aa¹⁰⁵ H SO₃H H H SO₃H H CONH₂ Isopropyl 2 2 2 2 1aa¹⁰⁶ H H SO₃H SO₃H H H 1aa¹⁰⁷ Methyl H SO₃H SO₃H H Methyl 1aa¹⁰⁸ OMe H SO₃H SO₃H H OMe 1aa¹⁰⁹ H SO₃H H H SO₃H H CONH₂ Sec-butyl 2 2 2 2 1aa¹¹⁰ H H SO₃H SO₃H H H 1aa¹¹¹ Methyl H SO₃H SO₃H H Methyl 1aa¹¹² OMe H SO₃H SO₃H H OMe 1aa¹¹³ H SO₃H H H SO₃H H CONH₂ 1aa¹¹⁴ H H SO₃H SO₃H H H 2-Methyl 2 2 2 2 1aa¹¹⁵ Methyl H SO₃H SO₃H H Methyl butyl 1aa¹¹⁶ OMe H SO₃H SO₃H H OMe 1aa¹¹⁷ H SO₃H H H SO₃H H CONH₂ 1-Ethyl 2 2 2 2 1aa¹¹⁸ H H SO₃H SO₃H H H propyl 1aa¹¹⁹ Methyl H SO₃H SO₃H H Methyl 1aa¹²⁰ OMe H SO₃H SO₃H H OMe 1aa¹²¹ H SO₃H H H SO₃H H CONH₂ 1,2-Dimethyl 2 2 2 2 1aa¹²² H H SO₃H SO₃H H H propyl 1aa¹²³ Methyl H SO₃H SO₃H H Methyl 1aa¹²⁴ OMe H SO₃H SO₃H H OMe 1aa¹²⁵ H SO₃H H H SO₃H H CONH₂ Tert-butyl 2 2 2 2 1aa¹²⁶ H H SO₃H SO₃H H H 1aa¹²⁷ Methyl H SO₃H SO₃H H Methyl 1aa¹²⁸ OMe H SO₃H SO₃H H OMe 1aa¹²⁹ H SO₃H H H SO₃H H CONH₂ 3-Methyl 2 2 2 2 1aa¹³⁰ H H SO₃H SO₃H H H butyl 1aa¹³¹ Methyl H SO₃H SO₃H H Methyl 1aa¹³² OMe H SO₃H SO₃H H OMe 1aa¹³³ H SO₃H H H SO₃H H CONH₂ Pentan-2-yl 2 2 2 2 1aa¹³⁴ H H SO₃H SO₃H H H 1aa¹³⁵ Methyl H SO₃H SO₃H H Methyl 1aa¹³⁶ OMe H SO₃H SO₃H H OMe 1aa¹³⁷ H SO₃H H H SO₃H H CONH₂ 2-Ethylhexyl 2 2 2 2 1aa¹³⁸ H H SO₃H SO₃H H H 1aa¹³⁹ Methyl H SO₃H SO₃H H Methyl 1aa¹⁴⁰ OMe H SO₃H SO₃H H OMe 1aa¹⁴¹ H SO₃H H H SO₃H H CONH₂ 2,2-Dimethyl 2 2 2 2 1aa¹⁴² H H SO₃H SO₃H H H propyl 1aa¹⁴³ Methyl H SO₃H SO₃H H Methyl 1aa¹⁴⁴ OMe H SO₃H SO₃H H OMe 1aa¹⁴⁵ H SO₃H H H SO₃H H CONH₂ Phenyl 2 2 2 2 1aa¹⁴⁶ H H SO₃H SO₃H H H 1aa¹⁴⁷ Methyl H SO₃H SO₃H H Methyl 1aa¹⁴⁸ OMe H SO₃H SO₃H H OMe 1aa¹⁴⁹ H SO₃H H H SO₃H H CONH₂ Benzyl 2 2 2 2 1aa¹⁵⁰ H H SO₃H SO₃H H H 1aa¹⁵¹ Methyl H SO₃H SO₃H H Methyl 1aa¹⁵² OMe H SO₃H SO₃H H OMe 1aa¹⁵³ H SO₃H H H SO₃H H CN H 3 4 3 4 1aa¹⁵⁴ H H SO₃H SO₃H H H 1aa¹⁵⁵ Methyl H SO₃H SO₃H H Methyl 1aa¹⁵⁶ OMe H SO₃H SO₃H H OMe 1aa¹⁵⁷ H SO₃H H H SO₃H H CN Ethyl 3 4 3 4 1aa¹⁵⁸ H H SO₃H SO₃H H H 1aa¹⁵⁹ Methyl H SO₃H SO₃H H Methyl 1aa¹⁶⁰ OMe H SO₃H SO₃H H OMe 1aa¹⁶¹ H SO₃H H H SO₃H H CN Propyl 3 4 3 4 1aa¹⁶² H H SO₃H SO₃H H H 1aa¹⁶³ Methyl H SO₃H SO₃H H Methyl 1aa¹⁶⁴ OMe H SO₃H SO₃H H OMe 1aa¹⁶⁵ H SO₃H H H SO₃H H CN Butyl 3 4 3 4 1aa¹⁶⁶ H H SO₃H SO₃H H H 1aa¹⁶⁷ Methyl H SO₃H SO₃H H Methyl 1aa¹⁶⁸ OMe H SO₃H SO₃H H OMe 1aa¹⁶⁹ H SO₃H H H SO₃H H CN Pentyl 3 4 3 4 1aa¹⁷⁰ H H SO₃H SO₃H H H 1aa¹⁷¹ Methyl H SO₃H SO₃H H Methyl 1aa¹⁷² OMe H SO₃H SO₃H H OMe 1aa¹⁷³ H SO₃H H H SO₃H H CN Cyclobutyl 3 4 3 4 1aa¹⁷⁴ H H SO₃H SO₃H H H 1aa¹⁷⁵ Methyl H SO₃H SO₃H H Methyl 1aa¹⁷⁶ OMe H SO₃H SO₃H H OMe 1aa¹⁷⁷ H SO₃H H H SO₃H H CN Cyclopentyl 3 4 3 4 1aa¹⁷⁸ H H SO₃H SO₃H H H 1aa¹⁷⁹ Methyl H SO₃H SO₃H H Methyl 1aa¹⁸⁰ OMe H SO₃H SO₃H H OMe 1aa¹⁸¹ H SO₃H H H SO₃H H CN Isopropyl 3 4 3 4 1aa¹⁸² H H SO₃H SO₃H H H 1aa¹⁸³ Methyl H SO₃H SO₃H H Methyl 1aa¹⁸⁴ OMe H SO₃H SO₃H H OMe 1aa¹⁸⁵ H SO₃H H H SO₃H H CN Sec-butyl 3 4 3 4 1aa¹⁸⁶ H H SO₃H SO₃H H H 1aa¹⁸⁷ Methyl H SO₃H SO₃H H Methyl 1aa¹⁸⁸ OMe H SO₃H SO₃H H OMe 1aa¹⁸⁹ H SO₃H H H SO₃H H CN 2-Methyl 3 4 3 4 1aa¹⁹⁰ H H SO₃H SO₃H H H butyl 1aa¹⁹¹ Methyl H SO₃H SO₃H H Methyl 1aa¹⁹² OMe H SO₃H SO₃H H OMe 1aa¹⁹³ H SO₃H H H SO₃H H CN 1-Ethyl 3 4 3 4 1aa¹⁹⁴ H H SO₃H SO₃H H H propyl 1aa¹⁹⁵ Methyl H SO₃H SO₃H H Methyl 1aa¹⁹⁶ OMe H SO₃H SO₃H H OMe 1aa¹⁹⁷ H SO₃H H H SO₃H H CN 1,2-Dimethyl 3 4 3 4 1aa¹⁹⁸ H H SO₃H SO₃H H H propyl 1aa¹⁹⁹ Methyl H SO₃H SO₃H H Methyl 1aa²⁰⁰ OMe H SO₃H SO₃H H OMe 1aa²⁰¹ H SO₃H H H SO₃H H CN Tert-butyl 3 4 3 4 1aa²⁰² H H SO₃H SO₃H H H 1aa²⁰³ Methyl H SO₃H SO₃H H Methyl 1aa²⁰⁴ OMe H SO₃H SO₃H H OMe 1aa²⁰⁵ H SO₃H H H SO₃H H CN 3-Methyl 3 4 3 4 1aa²⁰⁶ H H SO₃H SO₃H H H butyl 1aa²⁰⁷ Methyl H SO₃H SO₃H H Methyl 1aa²⁰⁸ OMe H SO₃H SO₃H H OMe 1aa²⁰⁹ H SO₃H H H SO₃H H CN Pentan-2-yl 3 4 3 4 1aa²¹⁰ H H SO₃H SO₃H H H 1aa²¹¹ Methyl H SO₃H SO₃H H Methyl 1aa²¹² OMe H SO₃H SO₃H H OMe 1aa²¹³ H SO₃H H H SO₃H H CN 2-Ethylhexyl 3 4 3 4 1aa²¹⁴ H H SO₃H SO₃H H H 1aa²¹⁵ Methyl H SO₃H SO₃H H Methyl 1aa²¹⁶ OMe H SO₃H SO₃H H OMe 1aa²¹⁷ H SO₃H H H SO₃H H CN 2,2-Dimethyl 3 4 3 4 1aa²¹⁸ H H SO₃H SO₃H H H propyl 1aa²¹⁹ Methyl H SO₃H SO₃H H Methyl 1aa²²⁰ OMe H SO₃H SO₃H H OMe 1aa²²¹ H SO₃H H H SO₃H H CN Phenyl 3 4 3 4 1aa²²² H H SO₃H SO₃H H H 1aa²²³ Methyl H SO₃H SO₃H H Methyl 1aa²²⁴ OMe H SO₃H SO₃H H OMe 1aa²²⁵ H SO₃H H H SO₃H H CN Benzyl 3 4 3 4 1aa²²⁶ H H SO₃H SO₃H H H 1aa²²⁷ Methyl H SO₃H SO₃H H Methyl 1aa²²⁸ OMe H SO₃H SO₃H H OMe 1aa²²⁹ H SO₃H H H SO₃H H CONH₂ H 3 4 3 4 1aa²³⁰ H H SO₃H SO₃H H H 1aa²³¹ Methyl H SO₃H SO₃H H Methyl 1aa²³² OMe H SO₃H SO₃H H OMe 1aa²³³ H SO₃H H H SO₃H H CONH₂ Ethyl 3 4 3 4 1aa²³⁴ H H SO₃H SO₃H H H 1aa²³⁵ Methyl H SO₃H SO₃H H Methyl 1aa²³⁶ OMe H SO₃H SO₃H H OMe 1aa²³⁷ H SO₃H H H SO₃H H CONH₂ Propyl 3 4 3 4 1aa²³⁸ H H SO₃H SO₃H H H 1aa²³⁹ Methyl H SO₃H SO₃H H Methyl 1aa²⁴⁰ OMe H SO₃H SO₃H H OMe 1aa²⁴¹ H SO₃H H H SO₃H H CONH₂ Butyl 3 4 3 4 1aa²⁴² H H SO₃H SO₃H H H 1aa²⁴³ Methyl H SO₃H SO₃H H Methyl 1aa²⁴⁴ OMe H SO₃H SO₃H H OMe 1aa²⁴⁵ H SO₃H H H SO₃H H CONH₂ Pentyl 3 4 3 4 1aa²⁴⁶ H H SO₃H SO₃H H H 1aa²⁴⁷ Methyl H SO₃H SO₃H H Methyl 1aa²⁴⁸ OMe H SO₃H SO₃H H OMe 1aa²⁴⁹ H SO₃H H H SO₃H H CONH₂ Cyclopentyl 3 4 3 4 1aa²⁵⁰ H H SO₃H SO₃H H H 1aa²⁵¹ Methyl H SO₃H SO₃H H Methyl 1aa²⁵² OMe H SO₃H SO₃H H OMe 1aa²⁵³ H SO₃H H H SO₃H H CONH₂ Cyclopentyl 3 4 3 4 1aa²⁵⁴ H H SO₃H SO₃H H H 1aa²⁵⁵ Methyl H SO₃H SO₃H H Methyl 1aa²⁵⁶ OMe H SO₃H SO₃H H OMe 1aa²⁵⁷ H SO₃H H H SO₃H H CONH₂ Isopropyl 3 4 3 4 1aa²⁵⁸ H H SO₃H SO₃H H H 1aa²⁵⁹ Methyl H SO₃H SO₃H H Methyl 1aa²⁶⁰ OMe H SO₃H SO₃H H OMe 1aa²⁶¹ H SO₃H H H SO₃H H CONH₂ Sec-butyl 3 4 3 4 1aa²⁶² H H SO₃H SO₃H H H 1aa²⁶³ Methyl H SO₃H SO₃H H Methyl 1aa²⁶⁴ OMe H SO₃H SO₃H H OMe 1aa²⁶⁵ H SO₃H H H SO₃H H CONH₂ 2-Methyl 3 4 3 4 1aa²⁶⁶ H H SO₃H SO₃H H H butyl 1aa²⁶⁷ Methyl H SO₃H SO₃H H Methyl 1aa²⁶⁸ OMe H SO₃H SO₃H H OMe 1aa²⁶⁹ H SO₃H H H SO₃H H CONH₂ 1-Ethyl 3 4 3 4 1aa²⁷⁰ H H SO₃H SO₃H H H propyl 1aa²⁷¹ Methyl H SO₃H SO₃H H Methyl 1aa²⁷² OMe H SO₃H SO₃H H OMe 1aa²⁷³ H SO₃H H H SO₃H H CONH₂ 1,2-Dimethyl 3 4 3 4 1aa²⁷⁴ H H SO₃H SO₃H H H propyl 1aa²⁷⁵ Methyl H SO₃H SO₃H H Methyl 1aa²⁷⁶ OMe H SO₃H SO₃H H OMe 1aa²⁷⁷ H SO₃H H H SO₃H H CONH₂ Tert-butyl 3 4 3 4 1aa²⁷⁸ H H SO₃H SO₃H H H 1aa²⁷⁹ Methyl H SO₃H SO₃H H Methyl 1aa²⁸⁰ OMe H SO₃H SO₃H H OMe 1aa²⁸¹ H SO₃H H H SO₃H H CONH₂ 3-Methyl 3 4 3 4 1aa²⁸² H H SO₃H SO₃H H H butyl 1aa²⁸³ Methyl H SO₃H SO₃H H Methyl 1aa²⁸⁴ OMe H SO₃H SO₃H H OMe 1aa²⁸⁵ H SO₃H H H SO₃H H CONH₂ Pentan-2-yl 3 4 3 4 1aa²⁸⁶ H H SO₃H SO₃H H H 1aa²⁸⁷ Methyl H SO₃H SO₃H H Methyl 1aa²⁸⁸ OMe H SO₃H SO₃H H OMe 1aa²⁸⁹ H SO₃H H H SO₃H H CONH₂ 2-Ethylhexyl 3 4 3 4 1aa²⁹⁰ H H SO₃H SO₃H H H 1aa²⁹¹ Methyl H SO₃H SO₃H H Methyl 1aa²⁹² OMe H SO₃H SO₃H H OMe 1aa²⁹³ H SO₃H H H SO₃H H CONH₂ 2,2-Dimethyl 3 4 3 4 1aa²⁹⁴ H H SO₃H SO₃H H H propyl 1aa²⁹⁵ Methyl H SO₃H SO₃H H Methyl 1aa²⁹⁶ OMe H SO₃H SO₃H H OMe 1aa²⁹⁷ H SO₃H H H SO₃H H CONH₂ Phenyl 3 4 3 4 1aa²⁹⁸ H H SO₃H SO₃H H H 1aa²⁹⁹ Methyl H SO₃H SO₃H H Methyl 1aa³⁰⁰ OMe H SO₃H SO₃H H OMe 1aa³⁰¹ H SO₃H H H SO₃H H CONH₂ Benzyl 3 4 3 4 1aa³⁰² H H SO₃H SO₃H H H 1aa³⁰³ Methyl H SO₃H SO₃H H Methyl 1aa³⁰⁴ OMe H SO₃H SO₃H H OMe 1aa³⁰⁵ H SO₃H H H SO₃H H CN H 3 3 3 3 1aa³⁰⁶ H H SO₃H SO₃H H H 1aa³⁰⁷ Methyl H SO₃H SO₃H H Methyl 1aa³⁰⁸ OMe H SO₃H SO₃H H OMe 1aa³⁰⁹ H SO₃H H H SO₃H H CN Ethyl 3 3 3 3 1aa³¹⁰ H H SO₃H SO₃H H H 1aa³¹¹ Methyl H SO₃H SO₃H H Methyl 1aa³¹² OMe H SO₃H SO₃H H OMe 1aa³¹³ H SO₃H H H SO₃H H CN Propyl 3 3 3 3 1aa³¹⁴ H H SO₃H SO₃H H H 1aa³¹⁵ Methyl H SO₃H SO₃H H Methyl 1aa³¹⁶ OMe H SO₃H SO₃H H OMe 1aa³¹⁷ H SO₃H H H SO₃H H CN Butyl 3 3 3 3 1aa³¹⁸ H H SO₃H SO₃H H H 1aa³¹⁹ Methyl H SO₃H SO₃H H Methyl 1aa³²⁰ OMe H SO₃H SO₃H H OMe 1aa³²¹ H SO₃H H H SO₃H H CN Pentyl 3 3 3 3 1aa³²² H H SO₃H SO₃H H H 1aa³²³ Methyl H SO₃H SO₃H H Methyl 1aa³²⁴ OMe H SO₃H SO₃H H OMe 1aa³²⁵ H SO₃H H H SO₃H H CN 1aa³²⁶ H H SO₃H SO₃H H H Cyclobutyl 3 3 3 3 1aa³²⁷ Methyl H SO₃H SO₃H H Methyl 1aa³²⁸ OMe H SO₃H SO₃H H OMe 1aa³²⁹ H SO₃H H H SO₃H H CN Cyclopentyl 3 3 3 3 1aa³³⁰ H H SO₃H SO₃H H H 1aa³³¹ Methyl H SO₃H SO₃H H Methyl 1aa³³² OMe H SO₃H SO₃H H OMe 1aa³³³ H SO₃H H H SO₃H H CN Isopropyl 3 3 3 3 1aa³³⁴ H H SO₃H SO₃H H H 1aa³³⁵ Methyl H SO₃H SO₃H H Methyl 1aa³³⁶ OMe H SO₃H SO₃H H OMe 1aa³³⁷ H SO₃H H H SO₃H H CN Sec-butyl 3 3 3 3 1aa³³⁸ H H SO₃H SO₃H H H 1aa³³⁹ Me H SO₃H SO₃H H Me 1aa³⁴⁰ OMe H SO₃H SO₃H H OMe 1aa³⁴¹ H SO₃H H H SO₃H H CN 2-Methyl 3 3 3 3 1aa³⁴² H H SO₃H SO₃H H H butyl 1aa³⁴³ Methyl H SO₃H SO₃H H Methyl 1aa³⁴⁴ OMe H SO₃H SO₃H H OMe 1aa³⁴⁵ H SO₃H H H SO₃H H CN 1-Ethyl 3 3 3 3 1aa³⁴⁶ H H SO₃H SO₃H H H propyl 1aa³⁴⁷ Methyl H SO₃H SO₃H H Methyl 1aa³⁴⁸ OMe H SO₃H SO₃H H OMe 1aa³⁴⁹ H SO₃H H H SO₃H H CN 1,2-Dimethyl 3 3 3 3 1aa³⁵⁰ H H SO₃H SO₃H H H propyl 1aa³⁵¹ Methyl H SO₃H SO₃H H Methyl 1aa³⁵² OMe H SO₃H SO₃H H OMe 1aa³⁵³ H SO₃H H H SO₃H H CN Tert-butyl 3 3 3 3 1aa³⁵⁴ H H SO₃H SO₃H H H 1aa³⁵⁵ Methyl H SO₃H SO₃H H Methyl 1aa³⁵⁶ OMe H SO₃H SO₃H H OMe 1aa³⁵⁷ H SO₃H H H SO₃H H CN 3-Methyl 3 3 3 3 1aa³⁵⁸ H H SO₃H SO₃H H H butyl 1aa³⁵⁹ Me H SO₃H SO₃H H Me 1aa³⁶⁰ OMe H SO₃H SO₃H H OMe 1aa³⁶¹ H SO₃H H H SO₃H H CN Pentan-2-yl 3 3 3 3 1aa³⁶² H H SO₃H SO₃H H H 1aa³⁶³ Methyl H SO₃H SO₃H H Methyl 1aa³⁶⁴ OMe H SO₃H SO₃H H OMe 1aa³⁶⁵ H SO₃H H H SO₃H H CN 2-Ethylhexyl 3 3 3 3 1aa³⁶⁶ H H SO₃H SO₃H H H 1aa³⁶⁷ Methyl H SO₃H SO₃H H Methyl 1aa³⁶⁸ OMe H SO₃H SO₃H H OMe 1aa³⁶⁹ H SO₃H H H SO₃H H CN 2,2-Dimethyl 3 3 3 3 1aa³⁷⁰ H H SO₃H SO₃H H H propyl 1aa³⁷¹ Methyl H SO₃H SO₃H H Methyl 1aa³⁷² OMe H SO₃H SO₃H H OMe 1aa³⁷³ H SO₃H H H SO₃H H CN Phenyl 3 3 3 3 1aa³⁷⁴ H H SO₃H SO₃H H H 1aa³⁷⁵ Methyl H SO₃H SO₃H H Methyl 1aa³⁷⁶ OMe H SO₃H SO₃H H OMe 1aa³⁷⁷ H SO₃H H H SO₃H H CN Benzyl 3 3 3 3 1aa³⁷⁸ H H SO₃H SO₃H H H 1aa³⁷⁹ Methyl H SO₃H SO₃H H Methyl 1aa³⁸⁰ OMe H SO₃H SO₃H H OMe 1aa³⁸¹ H SO₃H H H SO₃H H CONH₂ H 3 3 3 3 1aa³⁸² H H SO₃H SO₃H H H 1aa³⁸³ Methyl H SO₃H SO₃H H Methyl 1aa³⁸⁴ OMe H SO₃H SO₃H H OMe 1aa³⁸⁵ H SO₃H H H SO₃H H CONH₂ Ethyl 3 3 3 3 1aa³⁸⁶ H H SO₃H SO₃H H H 1aa³⁸⁷ Methyl H SO₃H SO₃H H Methyl 1aa³⁸⁸ OMe H SO₃H SO₃H H OMe 1aa³⁸⁹ H SO₃H H H SO₃H H CONH₂ Propyl 3 3 3 3 1aa³⁹⁰ H H SO₃H SO₃H H H 1aa³⁹¹ Methyl H SO₃H SO₃H H Methyl 1aa³⁹² OMe H SO₃H SO₃H H OMe 1aa³⁹³ H SO₃H H H SO₃H H CONH₂ Butyl 3 3 3 3 1aa³⁹⁴ H H SO₃H SO₃H H H 1aa³⁹⁵ Methyl H SO₃H SO₃H H Methyl 1aa³⁹⁶ OMe H SO₃H SO₃H H OMe 1aa³⁹⁷ H SO₃H H H SO₃H H CONH₂ Pentyl 3 3 3 3 1aa³⁹⁸ H H SO₃H SO₃H H H 1aa³⁹⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁰⁰ OMe H SO₃H SO₃H H OMe 1aa⁴⁰¹ H SO₃H H H SO₃H H CONH₂ Cyclobutyl 3 3 3 3 1aa⁴⁰² H H SO₃H SO₃H H H 1aa⁴⁰³ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁰⁴ OMe H SO₃H SO₃H H OMe 1aa⁴⁰⁵ H SO₃H H H SO₃H H CONH₂ Cyclopentyl 3 3 3 3 1aa⁴⁰⁶ H H SO₃H SO₃H H H 1aa⁴⁰⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁰⁸ OMe H SO₃H SO₃H H OMe 1aa⁴⁰⁹ H SO₃H H H SO₃H H CONH₂ Isopropyl 3 3 3 3 1aa⁴¹⁰ H H SO₃H SO₃H H H 1aa⁴¹¹ Methyl H SO₃H SO₃H H Methyl 1aa⁴¹² OMe H SO₃H SO₃H H OMe 1aa⁴¹³ H SO₃H H H SO₃H H CONH₂ Sec-butyl 3 3 3 3 1aa⁴¹⁴ H H SO₃H SO₃H H H 1aa⁴¹⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁴¹⁶ OMe H SO₃H SO₃H H OMe 1aa⁴¹⁷ H SO₃H H H SO₃H H CONH₂ 2-Methyl 3 3 3 3 1aa⁴¹⁸ H H SO₃H SO₃H H H butyl 1aa⁴¹⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁴²⁰ OMe H SO₃H SO₃H H OMe 1aa⁴²¹ H SO₃H H H SO₃H H CONH₂ 1-Ethyl 3 3 3 3 1aa⁴²² H H SO₃H SO₃H H H propyl 1aa⁴²³ Methyl H SO₃H SO₃H H Methyl 1aa⁴²⁴ OMe H SO₃H SO₃H H OMe 1aa⁴²⁵ H SO₃H H H SO₃H H CONH₂ 1,2-Dimethyl 3 3 3 3 1aa⁴²⁶ H H SO₃H SO₃H H H propyl 1aa⁴²⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁴²⁸ OMe H SO₃H SO₃H H OMe 1aa⁴²⁹ H SO₃H H H SO₃H H CONH₂ Tert-butyl 3 3 3 3 1aa⁴³⁰ H H SO₃H SO₃H H H 1aa⁴³¹ Methyl H SO₃H SO₃H H Methyl 1aa⁴³² OMe H SO₃H SO₃H H OMe 1aa⁴³³ H SO₃H H H SO₃H H CONH₂ 3-Methyl 3 3 3 3 1aa⁴³⁴ H H SO₃H SO₃H H H butyl 1aa⁴³⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁴³⁶ OMe H SO₃H SO₃H H OMe 1aa⁴³⁷ H SO₃H H H SO₃H H CONH₂ Pentan-2-yl 3 3 3 3 1aa⁴³⁸ H H SO₃H SO₃H H H 1aa⁴³⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁴⁰ OMe H SO₃H SO₃H H OMe 1aa⁴⁴¹ H SO₃H H H SO₃H H CONH₂ 2-Ethylhexyl 3 3 3 3 1aa⁴⁴² H H SO₃H SO₃H H H 1aa⁴⁴³ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁴⁴ OMe H SO₃H SO₃H H OMe 1aa⁴⁴⁵ H SO₃H H H SO₃H H CONH₂ 2,2-Dimethyl 3 3 3 3 1aa⁴⁴⁶ H H SO₃H SO₃H H H propyl 1aa⁴⁴⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁴⁸ OMe H SO₃H SO₃H H OMe 1aa⁴⁴⁹ H SO₃H H H SO₃H H CONH₂ Phenyl 3 3 3 3 1aa⁴⁵⁰ H H SO₃H SO₃H H H 1aa⁴⁵¹ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁵² OMe H SO₃H SO₃H H OMe 1aa⁴⁵³ H SO₃H H H SO₃H H CONH₂ Benzyl 3 3 3 3 1aa⁴⁵⁴ H H SO₃H SO₃H H H 1aa⁴⁵⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁵⁶ OMe H SO₃H SO₃H H OMe 1aa⁴⁵⁷ H SO₃H H H SO₃H H CN 2-Methoxy 2 2 2 2 1aa⁴⁵⁸ H H SO₃H SO₃H H H ethyl 1aa⁴⁵⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁶⁰ OMe H SO₃H SO₃H H OMe 1aa⁴⁶¹ H SO₃H H H SO₃H H CN 3-Methoxy 2 2 2 2 1aa⁴⁶² H H SO₃H SO₃H H H propyl 1aa⁴⁶³ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁶⁴ OMe H SO₃H SO₃H H OMe 1aa⁴⁶⁵ H SO₃H H H SO₃H H CN 2-Hydroxy 2 2 2 2 1aa⁴⁶⁶ H H SO₃H SO₃H H H ethyl 1aa⁴⁶⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁶⁸ OMe H SO₃H SO₃H H OMe 1aa⁴⁶⁹ H SO₃H H H SO₃H H CN 2-Fluoro 2 2 2 2 1aa⁴⁷⁰ H H SO₃H SO₃H H H ethyl 1aa⁴⁷¹ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁷² OMe H SO₃H SO₃H H OMe 1aa⁴⁷³ H SO₃H H H SO₃H H CN 2-Chloro 2 2 2 2 1aa⁴⁷⁴ H H SO₃H SO₃H H H ethyl 1aa⁴⁷⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁷⁶ OMe H SO₃H SO₃H H OMe 1aa⁴⁷⁷ H SO₃H H H SO₃H H CN 3-Chloro 2 2 2 2 1aa⁴⁷⁸ H H SO₃H SO₃H H H propyl 1aa⁴⁷⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁴⁸⁰ OMe H SO₃H SO₃H H OMe 1aa⁴⁸¹ H SO₃H H H SO₃H H CN 2-(2-Hydroxy- 2 2 2 2 1aa⁴⁸² H H SO₃H SO₃H H H ethyl sulfanyl)- 1aa⁴⁸³ Methyl H SO₃H SO₃H H Methyl ethyl 1aa⁴⁸⁴ OMe H SO₃H SO₃H H OMe 1aa⁴⁸⁵ H SO₃H H H SO₃H H CN 2-(2-tert-Butyl 2 2 2 2 1aa⁴⁸⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1aa⁴⁸⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1aa⁴⁸⁸ OMe H SO₃H SO₃H H OMe 1aa⁴⁸⁹ H SO₃H H H SO₃H H CN 3-(4-Hydroxy 2 2 2 2 1aa⁴⁹⁰ H H SO₃H SO₃H H H butoxy) 1aa⁴⁹¹ Methyl H SO₃H SO₃H H Methyl propyl 1aa⁴⁹² OMe H SO₃H SO₃H H OMe 1aa⁴⁹³ H SO3H H H SO3H H CN 2-(2-Hydroxy 2 2 2 2 1aa⁴⁹⁴ H H SO3H SO3H H H ethoxy)ethyl 1aa⁴⁹⁵ Methyl H SO3H SO3H H Methyl 1aa⁴⁹⁶ OMe H SO3H SO3H H OMe 1aa⁴⁹⁷ H SO₃H H H SO₃H H CN 4-(2-Hydroxy- 2 2 2 2 1aa⁴⁹⁸ H H SO₃H SO₃H H H ethane 1aa⁴⁹⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1aa⁵⁰⁰ OMe H SO₃H SO₃H H OMe 1aa⁵⁰¹ H SO₃H H H SO₃H H CN 3-(2-Phenoxy- 2 2 2 2 1aa⁵⁰² H H SO₃H SO₃H H H ethoxy)-propyl 1aa⁵⁰³ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁰⁴ OMe H SO₃H SO₃H H OMe 1aa⁵⁰⁵ H SO₃H H H SO₃H H CN 3-Isopropoxy- 2 2 2 2 1aa⁵⁰⁶ H H SO₃H SO₃H H H propyl 1aa⁵⁰⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁰⁸ OMe H SO₃H SO₃H H OMe 1aa⁵⁰⁹ H SO₃H H H SO₃H H CN 3-Ethoxy propyl 2 2 2 2 1aa⁵¹⁰ H H SO₃H SO₃H H H 1aa⁵¹¹ Methyl H SO₃H SO₃H H Methyl 1aa⁵¹² OMe H SO₃H SO₃H H OMe 1aa⁵¹³ H SO₃H H H SO₃H H CN 4-Ethoxy butyl 2 2 2 2 1aa⁵¹⁴ H H SO₃H SO₃H H H 1aa⁵¹⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁵¹⁶ OMe H SO₃H SO₃H H OMe 1aa⁵¹⁷ H SO₃H H H SO₃H H CONH₂ 2-Methoxy ethyl 2 2 2 2 1aa⁵¹⁸ H H SO₃H SO₃H H H 1aa⁵¹⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁵²⁰ OMe H SO₃H SO₃H H OMe 1aa⁵²¹ H SO₃H H H SO₃H H CONH₂ 3-Methoxy 2 2 2 2 1aa⁵²² H H SO₃H SO₃H H H propyl 1aa⁵²³ Methyl H SO₃H SO₃H H Methyl 1aa⁵²⁴ OMe H SO₃H SO₃H H OMe 1aa⁵²⁵ H SO₃H H H SO₃H H CONH₂ 2-Hydroxy ethyl 2 2 2 2 1aa⁵²⁶ H H SO₃H SO₃H H H 1aa⁵²⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁵²⁸ OMe H SO₃H SO₃H H OMe 1aa⁵²⁹ H SO₃H H H SO₃H H CONH₂ 2-Fluoro ethyl 2 2 2 2 1aa⁵³⁰ H H SO₃H SO₃H H H 1aa⁵³¹ Methyl H SO₃H SO₃H H Methyl 1aa⁵³² OMe H SO₃H SO₃H H OMe 1aa⁵³³ H SO₃H H H SO₃H H CONH₂ 2-Chloro ethyl 2 2 2 2 1aa⁵³⁴ H H SO₃H SO₃H H H 1aa⁵³⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁵³⁶ OMe H SO₃H SO₃H H OMe 1aa⁵³⁷ H SO₃H H H SO₃H H CONH₂ 3-Chloro propyl 2 2 2 2 1aa⁵³⁸ H H SO₃H SO₃H H H 1aa⁵³⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁴⁰ OMe H SO₃H SO₃H H OMe 1aa⁵⁴¹ H SO₃H H H SO₃H H CONH₂ 2-(2-Hydroxy- 2 2 2 2 1aa⁵⁴² H H SO₃H SO₃H H H ethyl sulfanyl)- 1aa⁵⁴³ Methyl H SO₃H SO₃H H Methyl ethyl 1aa⁵⁴⁴ OMe H SO₃H SO₃H H OMe 1aa⁵⁴⁵ H SO₃H H H SO₃H H CONH₂ 2-(2-tert-Butyl 2 2 2 2 1aa⁵⁴⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1aa⁵⁴⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1aa⁵⁴⁸ OMe H SO₃H SO₃H H OMe 1aa⁵⁴⁹ H SO₃H H H SO₃H H CONH₂ 3-(4-Hydroxy 2 2 2 2 1aa⁵⁵⁰ H H SO₃H SO₃H H H butoxy) 1aa⁵⁵¹ Methyl H SO₃H SO₃H H Methyl propyl 1aa⁵⁵² OMe H SO₃H SO₃H H OMe 1aa⁵⁵³ H SO3H H H SO3H H CONH₂ 2-(2-Hydroxy 2 2 2 2 1aa⁵⁵⁴ H H SO3H SO3H H H ethoxy)ethyl 1aa⁵⁵⁵ Methyl H SO3H SO3H H Methyl 1aa⁵⁵⁶ OMe H SO3H SO3H H OMe 1aa⁵⁵⁷ H SO₃H H H SO₃H H CONH₂ 4-(2-Hydroxy- 2 2 2 2 1aa⁵⁵⁸ H H SO₃H SO₃H H H ethane 1aa⁵⁵⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1aa⁵⁶⁰ OMe H SO₃H SO₃H H OMe 1aa⁵⁶¹ H SO₃H H H SO₃H H CONH₂ 3-(2-Phenoxy- 2 2 2 2 1aa⁵⁶² H H SO₃H SO₃H H H ethoxy)-propyl 1aa⁵⁶³ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁶⁴ OMe H SO₃H SO₃H H OMe 1aa⁵⁶⁵ H SO₃H H H SO₃H H CONH₂ 3-Isopropoxy- 2 2 2 2 1aa⁵⁶⁶ H H SO₃H SO₃H H H propyl 1aa⁵⁶⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁶⁸ OMe H SO₃H SO₃H H OMe 1aa⁵⁶⁹ H SO₃H H H SO₃H H CONH₂ 3-Ethoxy-propyl 2 2 2 2 1aa⁵⁷⁰ H H SO₃H SO₃H H H 1aa⁵⁷¹ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁷² OMe H SO₃H SO₃H H OMe 1aa⁵⁷³ H SO₃H H H SO₃H H CONH₂ 4-Ethoxy butyl 2 2 2 2 1aa⁵⁷⁴ H H SO₃H SO₃H H H 1aa⁵⁷⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁷⁶ OMe H SO₃H SO₃H H OMe 1aa⁵⁷⁷ H SO₃H H H SO₃H H CN 2-Methoxy ethyl 3 4 3 4 1aa⁵⁷⁸ H H SO₃H SO₃H H H 1aa⁵⁷⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁸⁰ OMe H SO₃H SO₃H H OMe 1aa⁵⁸¹ H SO₃H H H SO₃H H CN 3-Methoxy 3 4 3 4 1aa⁵⁸² H H SO₃H SO₃H H H propyl 1aa⁵⁸³ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁸⁴ OMe H SO₃H SO₃H H OMe 1aa⁵⁸⁵ H SO₃H H H SO₃H H CN 2-Hydroxy ethyl 3 4 3 4 1aa⁵⁸⁶ H H SO₃H SO₃H H H 1aa⁵⁸⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁸⁸ OMe H SO₃H SO₃H H OMe 1aa⁵⁸⁹ H SO₃H H H SO₃H H CN 2-Fluoro ethyl 3 4 3 4 1aa⁵⁹⁰ H H SO₃H SO₃H H H 1aa⁵⁹¹ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁹² OMe H SO₃H SO₃H H OMe 1aa⁵⁹³ H SO₃H H H SO₃H H CN 2-Chloro ethyl 3 4 3 4 1aa⁵⁹⁴ H H SO₃H SO₃H H H 1aa⁵⁹⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁵⁹⁶ OMe H SO₃H SO₃H H OMe 1aa⁵⁹⁷ H SO₃H H H SO₃H H CN 3-Chloro propyl 3 4 3 4 1aa⁵⁹⁸ H H SO₃H SO₃H H H 1aa⁵⁹⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁰⁰ OMe H SO₃H SO₃H H OMe 1aa⁶⁰¹ H SO₃H H H SO₃H H CN 2-(2-Hydroxy- 3 4 3 4 1aa⁶⁰² H H SO₃H SO₃H H H ethyl sulfanyl)- 1aa⁶⁰³ Methyl H SO₃H SO₃H H Methyl ethyl 1aa⁶⁰⁴ OMe H SO₃H SO₃H H OMe 1aa⁶⁰⁵ H SO₃H H H SO₃H H CN 2-(2-tert-Butyl 3 4 3 4 1aa⁶⁰⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1aa⁶⁰⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1aa⁶⁰⁸ OMe H SO₃H SO₃H H OMe 1aa⁶⁰⁹ H SO₃H H H SO₃H H CN 3-(4-Hydroxy 3 4 3 4 1aa⁶¹⁰ H H SO₃H SO₃H H H butoxy) 1aa⁶¹¹ Methyl H SO₃H SO₃H H Methyl propyl 1aa⁶¹² OMe H SO₃H SO₃H H OMe 1aa⁶¹³ H SO3H H H SO3H H CN 2-(2-Hydroxy 3 4 3 4 1aa⁶¹⁴ H H SO3H SO3H H H ethoxy)ethyl 1aa⁶¹⁵ Methyl H SO3H SO3H H Methyl 1aa⁶¹⁶ OMe H SO3H SO3H H OMe 1aa⁶¹⁷ H SO₃H H H SO₃H H CN 4-(2-Hydroxy- 3 4 3 4 1aa⁶¹⁸ H H SO₃H SO₃H H H ethane 1aa⁶¹⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1aa⁶²⁰ OMe H SO₃H SO₃H H OMe 1aa⁶²¹ H SO₃H H H SO₃H H CN 3-(2-Phenoxy- 3 4 3 4 1aa⁶²² H H SO₃H SO₃H H H ethoxy)-propyl 1aa⁶²³ Methyl H SO₃H SO₃H H Methyl 1aa⁶²⁴ OMe H SO₃H SO₃H H OMe 1aa⁶²⁵ H SO₃H H H SO₃H H CN 3-Isopropoxy- 3 4 3 4 1aa⁶²⁶ H H SO₃H SO₃H H H propyl 1aa⁶²⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁶²⁸ OMe H SO₃H SO₃H H OMe 1aa⁶²⁹ H SO₃H H H SO₃H H CN 3-Ethoxy propyl 3 4 3 4 1aa⁶³⁰ H H SO₃H SO₃H H H 1aa⁶³¹ Methyl H SO₃H SO₃H H Methyl 1aa⁶³² OMe H SO₃H SO₃H H OMe 1aa⁶³³ H SO₃H H H SO₃H H CN 4-Ethoxy butyl 3 4 3 4 1aa⁶³⁴ H H SO₃H SO₃H H H 1aa⁶³⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁶³⁶ OMe H SO₃H SO₃H H OMe 1aa⁶³⁷ H SO₃H H H SO₃H H CONH₂ 2-Methoxy ethyl 3 4 3 4 1aa⁶³⁸ H H SO₃H SO₃H H H 1aa⁶³⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁴⁰ OMe H SO₃H SO₃H H OMe 1aa⁶⁴¹ H SO₃H H H SO₃H H CONH₂ 3-Methoxy 3 4 3 4 1aa⁶⁴² H H SO₃H SO₃H H H propyl 1aa⁶⁴³ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁴⁴ OMe H SO₃H SO₃H H OMe 1aa⁶⁴⁵ H SO₃H H H SO₃H H CONH₂ 2-Hydroxy ethyl 3 4 3 4 1aa⁶⁴⁶ H H SO₃H SO₃H H H 1aa⁶⁴⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁴⁸ OMe H SO₃H SO₃H H OMe 1aa⁶⁴⁹ H SO₃H H H SO₃H H CONH₂ 2-Fluoro ethyl 3 4 3 4 1aa⁶⁵⁰ H H SO₃H SO₃H H H 1aa⁶⁵¹ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁵² OMe H SO₃H SO₃H H OMe 1aa⁶⁵³ H SO₃H H H SO₃H H CONH₂ 2-Chloro ethyl 3 4 3 4 1aa⁶⁵⁴ H H SO₃H SO₃H H H 1aa⁶⁵⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁵⁶ OMe H SO₃H SO₃H H OMe 1aa⁶⁵⁷ H SO₃H H H SO₃H H CONH₂ 3-Chloro propyl 3 4 3 4 1aa⁶⁵⁸ H H SO₃H SO₃H H H 1aa⁶⁵⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁶⁰ OMe H SO₃H SO₃H H OMe 1aa⁶⁶¹ H SO₃H H H SO₃H H CONH₂ 2-(2-Hydroxy- 3 4 3 4 1aa⁶⁶² H H SO₃H SO₃H H H ethyl sulfanyl)- 1aa⁶⁶³ Methyl H SO₃H SO₃H H Methyl ethyl 1aa⁶⁶⁴ OMe H SO₃H SO₃H H OMe 1aa⁶⁶⁵ H SO₃H H H SO₃H H CONH₂ 2-(2-tert-Butyl 3 4 3 4 1aa⁶⁶⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1aa⁶⁶⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1aa⁶⁶⁸ OMe H SO₃H SO₃H H OMe 1aa⁶⁶⁹ H SO₃H H H SO₃H H CONH₂ 3-(4-Hydroxy 3 4 3 4 1aa⁶⁷⁰ H H SO₃H SO₃H H H butoxy) 1aa⁶⁷¹ Methyl H SO₃H SO₃H H Methyl propyl 1aa⁶⁷² OMe H SO₃H SO₃H H OMe 1aa⁶⁷³ H SO3H H H SO3H H CONH₂ 2-(2-Hydroxy 3 4 3 4 1aa⁶⁷⁴ H H SO3H SO3H H H ethoxy)ethyl 1aa⁶⁷⁵ Methyl H SO3H SO3H H Methyl 1aa⁶⁷⁶ OMe H SO3H SO3H H OMe 1aa⁶⁷⁷ H SO₃H H H SO₃H H CONH₂ 4-(2-Hydroxy- 3 4 3 4 1aa⁶⁷⁸ H H SO₃H SO₃H H H ethane 1aa⁶⁷⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1aa⁶⁸⁰ OMe H SO₃H SO₃H H OMe 1aa⁶⁸¹ H SO₃H H H SO₃H H CONH₂ 3-(2-Phenoxy- 3 4 3 4 1aa⁶⁸² H H SO₃H SO₃H H H ethoxy)-propyl 1aa⁶⁸³ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁸⁴ OMe H SO₃H SO₃H H OMe 1aa⁶⁸⁵ H SO₃H H H SO₃H H CONH₂ 3-Isopropoxy- 3 4 3 4 1aa⁶⁸⁶ H H SO₃H SO₃H H H propyl 1aa⁶⁸⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁸⁸ OMe H SO₃H SO₃H H OMe 1aa⁶⁸⁹ H SO₃H H H SO₃H H CONH₂ 3-Ethoxy-propyl 3 4 3 4 1aa⁶⁹⁰ H H SO₃H SO₃H H H 1aa⁶⁹¹ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁹² OMe H SO₃H SO₃H H OMe 1aa⁶⁹³ H SO₃H H H SO₃H H CONH₂ 3-Ethoxybutyl 3 4 3 4 1aa⁶⁹⁴ H H SO₃H SO₃H H H 1aa⁶⁹⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁶⁹⁶ OMe H SO₃H SO₃H H OMe 1aa⁶⁹⁷ H SO₃H H H SO₃H H CN 2-Methoxy ethyl 3 3 3 3 1aa⁶⁹⁸ H H SO₃H SO₃H H H 1aa⁶⁹⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁰⁰ OMe H SO₃H SO₃H H OMe 1aa⁷⁰¹ H SO₃H H H SO₃H H CN 3-Methoxy 3 3 3 3 1aa⁷⁰² H H SO₃H SO₃H H H propyl 1aa⁷⁰³ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁰⁴ OMe H SO₃H SO₃H H OMe 1aa⁷⁰⁵ H SO₃H H H SO₃H H CN 2-Hydroxy ethyl 3 3 3 3 1aa⁷⁰⁶ H H SO₃H SO₃H H H 1aa⁷⁰⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁰⁸ OMe H SO₃H SO₃H H OMe 1aa⁷⁰⁹ H SO₃H H H SO₃H H CN 2-Fluoro ethyl 3 3 3 3 1aa⁷¹⁰ H H SO₃H SO₃H H H 1aa⁷¹¹ Methyl H SO₃H SO₃H H Methyl 1aa⁷¹² OMe H SO₃H SO₃H H OMe 1aa⁷¹³ H SO₃H H H SO₃H H CN 2-Chloro ethyl 3 3 3 3 1aa⁷¹⁴ H H SO₃H SO₃H H H 1aa⁷¹⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁷¹⁶ OMe H SO₃H SO₃H H OMe 1aa⁷¹⁷ H SO₃H H H SO₃H H CN 3-Chloro propyl 3 3 3 3 1aa⁷¹⁸ H H SO₃H SO₃H H H 1aa⁷¹⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁷²⁰ OMe H SO₃H SO₃H H OMe 1aa⁷²¹ H SO₃H H H SO₃H H CN 2-(2-Hydroxy- 3 3 3 3 1aa⁷²² H H SO₃H SO₃H H H ethyl sulfanyl)- 1aa⁷²³ Methyl H SO₃H SO₃H H Methyl ethyl 1aa⁷²⁴ OMe H SO₃H SO₃H H OMe 1aa⁷²⁵ H SO₃H H H SO₃H H CN 2-(2-tert-Butyl 3 3 3 3 1aa⁷²⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1aa⁷²⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1aa⁷²⁸ OMe H SO₃H SO₃H H OMe 1aa⁷²⁹ H SO₃H H H SO₃H H CN 3-(4-Hydroxy 3 3 3 3 1aa⁷³⁰ H H SO₃H SO₃H H H butoxy) 1aa⁷³¹ Methyl H SO₃H SO₃H H Methyl propyl 1aa⁷³² OMe H SO₃H SO₃H H OMe 1aa⁷³³ H SO3H H H SO3H H CN 2-(2-Hydroxy 3 3 3 3 1aa⁷³⁴ H H SO3H SO3H H H ethoxy)ethyl 1aa⁷³⁵ Methyl H SO3H SO3H H Methyl 1aa⁷³⁶ OMe H SO3H SO3H H OMe 1aa⁷³⁷ H SO₃H H H SO₃H H CN 4-(2-Hydroxy- 3 3 3 3 1aa⁷³⁸ H H SO₃H SO₃H H H ethane 1aa⁷³⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1aa⁷⁴⁰ OMe H SO₃H SO₃H H OMe 1aa⁷⁴¹ H SO₃H H H SO₃H H CN 3-(2-Phenoxy- 3 3 3 3 1aa⁷⁴² H H SO₃H SO₃H H H ethoxy)-propyl 1aa⁷⁴³ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁴⁴ OMe H SO₃H SO₃H H OMe 1aa⁷⁴⁵ H SO₃H H H SO₃H H CN 3-Isopropoxy- 3 3 3 3 1aa⁷⁴⁶ H H SO₃H SO₃H H H propyl 1aa⁷⁴⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁴⁸ OMe H SO₃H SO₃H H OMe 1aa⁷⁴⁹ H SO₃H H H SO₃H H CN 3-Ethoxy propyl 3 3 3 3 1aa⁷⁵⁰ H H SO₃H SO₃H H H 1aa⁷⁵¹ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁵² OMe H SO₃H SO₃H H OMe 1aa⁷⁵³ H SO₃H H H SO₃H H CN 4-Ethoxy butyl 3 3 3 3 1aa⁷⁵⁴ H H SO₃H SO₃H H H 1aa⁷⁵⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁵⁶ OMe H SO₃H SO₃H H OMe 1aa⁷⁵⁷ H SO₃H H H SO₃H H CONH₂ 2-Methoxy ethyl 3 3 3 3 1aa⁷⁵⁸ H H SO₃H SO₃H H H 1aa⁷⁵⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁶⁰ OMe H SO₃H SO₃H H OMe 1aa⁷⁶¹ H SO₃H H H SO₃H H CONH₂ 3-Methoxy 3 3 3 3 1aa⁷⁶² H H SO₃H SO₃H H H propyl 1aa⁷⁶³ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁶⁴ OMe H SO₃H SO₃H H OMe 1aa⁷⁶⁵ H SO₃H H H SO₃H H CONH₂ 2-Hydroxy ethyl 3 3 3 3 1aa⁷⁶⁶ H H SO₃H SO₃H H H 1aa⁷⁶⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁶⁸ OMe H SO₃H SO₃H H OMe 1aa⁷⁶⁹ H SO₃H H H SO₃H H CONH₂ 2-Fluoro ethyl 3 3 3 3 1aa⁷⁷⁰ H H SO₃H SO₃H H H 1aa⁷⁷¹ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁷² OMe H SO₃H SO₃H H OMe 1aa⁷⁷³ H SO₃H H H SO₃H H CONH₂ 2-Chloro ethyl 3 3 3 3 1aa⁷⁷⁴ H H SO₃H SO₃H H H 1aa⁷⁷⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁷⁶ OMe H SO₃H SO₃H H OMe 1aa⁷⁷⁷ H SO₃H H H SO₃H H CONH₂ 3-Chloro propyl 3 3 3 3 1aa⁷⁷⁸ H H SO₃H SO₃H H H 1aa⁷⁷⁹ Methyl H SO₃H SO₃H H Methyl 1aa⁷⁸⁰ OMe H SO₃H SO₃H H OMe 1aa⁷⁸¹ H SO₃H H H SO₃H H CONH₂ 2-(2-Hydroxy- 3 3 3 3 1aa⁷⁸² H H SO₃H SO₃H H H ethyl sulfanyl)- 1aa⁷⁸³ Methyl H SO₃H SO₃H H Methyl ethyl 1aa⁷⁸⁴ OMe H SO₃H SO₃H H OMe 1aa⁷⁸⁵ H SO₃H H H SO₃H H CONH₂ 2-(2-tert-Butyl 3 3 3 3 1aa⁷⁸⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1aa⁷⁸⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1aa⁷⁸⁸ OMe H SO₃H SO₃H H OMe 1aa⁷⁸⁹ H SO₃H H H SO₃H H CONH₂ 3-(4-Hydroxy 3 3 3 3 1aa⁷⁹⁰ H H SO₃H SO₃H H H butoxy) 1aa⁷⁹¹ Methyl H SO₃H SO₃H H Methyl propyl 1aa⁷⁹² OMe H SO₃H SO₃H H OMe 1aa⁷⁹³ H SO3H H H SO3H H CONH₂ 2-(2-Hydroxy 3 3 3 3 1aa⁷⁹⁴ H H SO3H SO3H H H ethoxy)ethyl 1aa⁷⁹⁵ Methyl H SO3H SO3H H Methyl 1aa⁷⁹⁶ OMe H SO3H SO3H H OMe 1aa⁷⁹⁷ H SO₃H H H SO₃H H CONH₂ 4-(2-Hydroxy- 3 3 3 3 1aa⁷⁹⁸ H H SO₃H SO₃H H H ethane 1aa⁷⁹⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1aa⁸⁰⁰ OMe H SO₃H SO₃H H OMe 1aa⁸⁰¹ H SO₃H H H SO₃H H CONH₂ 3-(2-Phenoxy- 3 3 3 3 1aa⁸⁰² H H SO₃H SO₃H H H ethoxy)-propyl 1aa⁸⁰³ Methyl H SO₃H SO₃H H Methyl 1aa⁸⁰⁴ OMe H SO₃H SO₃H H OMe 1aa⁸⁰⁵ H SO₃H H H SO₃H H CONH₂ 3-Isopropoxy- 3 3 3 3 1aa⁸⁰⁶ H H SO₃H SO₃H H H propyl 1aa⁸⁰⁷ Methyl H SO₃H SO₃H H Methyl 1aa⁸⁰⁸ OMe H SO₃H SO₃H H OMe 1aa⁸⁰⁹ H SO₃H H H SO₃H H CONH₂ 3-Ethoxy-propyl 3 3 3 3 1aa⁸¹⁰ H H SO₃H SO₃H H H 1aa⁸¹¹ Methyl H SO₃H SO₃H H Methyl 1aa⁸¹² OMe H SO₃H SO₃H H OMe 1aa⁸¹³ H SO₃H H H SO₃H H CONH₂ 4-Ethoxy butyl 3 3 3 3 1aa⁸¹⁴ H H SO₃H SO₃H H H 1aa⁸¹⁵ Methyl H SO₃H SO₃H H Methyl 1aa⁸¹⁶ OMe H SO₃H SO₃H H OMe

Further preferred embodiments of the present invention are dyes of formula (1ab)

wherein R^(1ab), R^(2ab), R^(3ab), R^(4ab), R^(5ab), R^(6ab), R^(7ab) and R^(8ab) independent of each other is SO₃M, hydrogen, alkyl or alkoxy, whereby at least two of them are SO₃M, R^(9ab) and R^(18ab) independent of each other is cyano or carbamoyl, R^(10ab) and R^(19ab) is methyl, m, n, o and p independent of each other is an integer and is 2, 3 or 4, R^(11ab), R^(13ab), R^(14ab), R^(15ab), R^(16ab), R^(17ab), R^(20ab), R^(22ab), R^(23ab), R^(24ab), R^(25ab), and R^(26ab) is hydrogen R^(12ab) and R^(21ab) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylproyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-methoxyethyl, 3-methoxypropyl, 2-hydroxyethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 6-hydroxy-1-[2-(2-hydroxyethylsulfanyl)-ethyl], 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(ethylsulfonyl)ethanol, 2-hydroxyethoxypropyl, 2-hydroxyethoxyethyl, 2-(ethyl sulfonyl) ethanol, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, and M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of preferred dyes of the formula (1ab) are the compounds of the formulae (1ab¹ to 1ab⁸¹⁶), wherein R^(2ab) and R^(7ab) is hydrogen:

Structure R^(1ab) R^(3ab) R^(4ab) R^(5ab) R^(6ab) R^(8ab) R^(9ab)/R^(18ab) R^(12ab)/R^(21ab) m n o p 1ab¹ H SO₃H H H SO₃H H CN H 2 2 2 2 1ab² H H SO₃H SO₃H H H 1ab³ Methyl H SO₃H SO₃H H Methyl 1ab⁴ OMe H SO₃H SO₃H H OMe 1ab⁵ H SO₃H H H SO₃H H CN Ethyl 2 2 2 2 1ab⁶ H H SO₃H SO₃H H H 1ab⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁸ OMe H SO₃H SO₃H H OMe 1ab⁹ H SO₃H H H SO₃H H CN Propyl 2 2 2 2 1ab¹⁰ H H SO₃H SO₃H H H 1ab¹¹ Methyl H SO₃H SO₃H H Methyl 1ab¹² OMe H SO₃H SO₃H H OMe 1ab¹³ H SO₃H H H SO₃H H CN Butyl 2 2 2 2 1ab¹⁴ H H SO₃H SO₃H H H 1ab¹⁵ Methyl H SO₃H SO₃H H Methyl 1ab¹⁶ OMe H SO₃H SO₃H H OMe 1ab¹⁷ H SO₃H H H SO₃H H CN Pentyl 2 2 2 2 1ab¹⁸ H H SO₃H SO₃H H H 1ab¹⁹ Methyl H SO₃H SO₃H H Methyl 1ab²⁰ OMe H SO₃H SO₃H H OMe 1ab²¹ H SO₃H H H SO₃H H CN Cyclobutyl 2 2 2 2 1ab²² H H SO₃H SO₃H H H 1ab²³ Methyl H SO₃H SO₃H H Methyl 1ab²⁴ OMe H SO₃H SO₃H H OMe 1ab²⁵ H SO₃H H H SO₃H H CN Cyclopentyl 2 2 2 2 1ab²⁶ H H SO₃H SO₃H H H 1ab²⁷ Methyl H SO₃H SO₃H H Methyl 1ab²⁸ OMe H SO₃H SO₃H H OMe 1ab²⁹ H SO₃H H H SO₃H H CN Isopropyl 2 2 2 2 1ab³⁰ H H SO₃H SO₃H H H 1ab³¹ Methyl H SO₃H SO₃H H Methyl 1ab³² OMe H SO₃H SO₃H H OMe 1ab³³ H SO₃H H H SO₃H H CN Sec-butyl 2 2 2 2 1ab³⁴ H H SO₃H SO₃H H H 1ab³⁵ Methyl H SO₃H SO₃H H Methyl 1ab³⁶ OMe H SO₃H SO₃H H OMe 1ab³⁷ H SO₃H H H SO₃H H CN 2-Methyl butyl 2 2 2 2 1ab³⁸ H H SO₃H SO₃H H H 1ab³⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁰ OMe H SO₃H SO₃H H OMe 1ab⁴¹ H SO₃H H H SO₃H H CN 1-Ethyl propyl 2 2 2 2 1ab⁴² H H SO₃H SO₃H H H 1ab⁴³ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁴ OMe H SO₃H SO₃H H OMe 1ab⁴⁵ H SO₃H H H SO₃H H CN 1,2-Dimethyl 2 2 2 2 1ab⁴⁶ H H SO₃H SO₃H H H propyl 1ab⁴⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁸ OMe H SO₃H SO₃H H OMe 1ab⁴⁹ H SO₃H H H SO₃H H CN Tert-butyl 2 2 2 2 1ab⁵⁰ H H SO₃H SO₃H H H 1ab⁵¹ Methyl H SO₃H SO₃H H Methyl 1ab⁵² OMe H SO₃H SO₃H H OMe 1ab⁵³ H SO₃H H H SO₃H H CN 3-Methyl butyl 2 2 2 2 1ab⁵⁴ H H SO₃H SO₃H H H 1ab⁵⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁶ OMe H SO₃H SO₃H H OMe 1ab⁵⁷ H SO₃H H H SO₃H H CN Pentan-2-yl 2 2 2 2 1ab⁵⁸ H H SO₃H SO₃H H H 1ab⁵⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁰ OMe H SO₃H SO₃H H OMe 1ab⁶¹ H SO₃H H H SO₃H H CN 2-Ethylhexyl 2 2 2 2 1ab⁶² H H SO₃H SO₃H H H 1ab⁶³ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁴ OMe H SO₃H SO₃H H OMe 1ab⁶⁵ H SO₃H H H SO₃H H CN 2,2-Dimethyl 2 2 2 2 1ab⁶⁶ H H SO₃H SO₃H H H propyl 1ab⁶⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁸ OMe H SO₃H SO₃H H OMe 1ab⁶⁹ H SO₃H H H SO₃H H CN Phenyl 2 2 2 2 1ab⁷⁰ H H SO₃H SO₃H H H 1ab⁷¹ Methyl H SO₃H SO₃H H Methyl 1ab⁷² OMe H SO₃H SO₃H H OMe 1ab⁷³ H SO₃H H H SO₃H H CN Benzyl 2 2 2 2 1ab⁷⁴ H H SO₃H SO₃H H H 1ab⁷⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁶ OMe H SO₃H SO₃H H OMe 1ab⁷⁷ H SO₃H H H SO₃H H CONH₂ H 2 2 2 2 1ab⁷⁸ H H SO₃H SO₃H H H 1ab⁷⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁸⁰ OMe H SO₃H SO₃H H OMe 1ab⁸¹ H SO₃H H H SO₃H H CONH₂ Ethyl 2 2 2 2 1ab⁸² H H SO₃H SO₃H H H 1ab⁸³ Methyl H SO₃H SO₃H H Methyl 1ab⁸⁴ OMe H SO₃H SO₃H H OMe 1ab⁸⁵ H SO₃H H H SO₃H H CONH₂ Propyl 2 2 2 2 1ab⁸⁶ H H SO₃H SO₃H H H 1ab⁸⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁸⁸ OMe H SO₃H SO₃H H OMe 1ab⁸⁹ H SO₃H H H SO₃H H CONH₂ Butyl 2 2 2 2 1ab⁹⁰ H H SO₃H SO₃H H H 1ab⁹¹ Methyl H SO₃H SO₃H H Methyl 1ab⁹² OMe H SO₃H SO₃H H OMe 1ab⁹³ H SO₃H H H SO₃H H CONH₂ Pentyl 2 2 2 2 1ab⁹⁴ H H SO₃H SO₃H H H 1ab⁹⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁹⁶ OMe H SO₃H SO₃H H OMe 1ab⁹⁷ H SO₃H H H SO₃H H CONH₂ Cyclobutyl 2 2 2 2 1ab⁹⁸ H H SO₃H SO₃H H H 1ab⁹⁹ Methyl H SO₃H SO₃H H Methyl 1ab¹⁰⁰ OMe H SO₃H SO₃H H OMe 1ab¹⁰¹ H SO₃H H H SO₃H H CONH₂ Cyclopentyl 2 2 2 2 1ab¹⁰² H H SO₃H SO₃H H H 1ab¹⁰³ Methyl H SO₃H SO₃H H Methyl 1ab¹⁰⁴ OMe H SO₃H SO₃H H OMe 1ab¹⁰⁵ H SO₃H H H SO₃H H CONH₂ Isopropyl 2 2 2 2 1ab¹⁰⁶ H H SO₃H SO₃H H H 1ab¹⁰⁷ Methyl H SO₃H SO₃H H Methyl 1ab¹⁰⁸ OMe H SO₃H SO₃H H OMe 1ab¹⁰⁹ H SO₃H H H SO₃H H CONH₂ Sec-butyl 2 2 2 2 1ab¹¹⁰ H H SO₃H SO₃H H H 1ab¹¹¹ Methyl H SO₃H SO₃H H Methyl 1ab¹¹² OMe H SO₃H SO₃H H OMe 1ab¹¹³ H SO₃H H H SO₃H H CONH₂ 2-Methyl butyl 2 2 2 2 1ab¹¹⁴ H H SO₃H SO₃H H H 1ab¹¹⁵ Methyl H SO₃H SO₃H H Methyl 1ab¹¹⁶ OMe H SO₃H SO₃H H OMe 1ab¹¹⁷ H SO₃H H H SO₃H H CONH₂ 1-Ethyl propyl 2 2 2 2 1ab¹¹⁸ H H SO₃H SO₃H H H 1ab¹¹⁹ Methyl H SO₃H SO₃H H Methyl 1ab¹²⁰ OMe H SO₃H SO₃H H OMe 1ab¹²¹ H SO₃H H H SO₃H H CONH₂ 1,2-Dimethyl 2 2 2 2 1ab¹²² H H SO₃H SO₃H H H propyl 1ab¹²³ Methyl H SO₃H SO₃H H Methyl 1ab¹²⁴ OMe H SO₃H SO₃H H OMe 1ab¹²⁵ H SO₃H H H SO₃H H CONH₂ Tert-butyl 2 2 2 2 1ab¹²⁶ H H SO₃H SO₃H H H 1ab¹²⁷ Methyl H SO₃H SO₃H H Methyl 1ab¹²⁸ OMe H SO₃H SO₃H H OMe 1ab¹²⁹ H SO₃H H H SO₃H H CONH₂ 3-Methyl butyl 2 2 2 2 1ab¹³⁰ H H SO₃H SO₃H H H 1ab¹³¹ Methyl H SO₃H SO₃H H Methyl 1ab¹³² OMe H SO₃H SO₃H H OMe 1ab¹³³ H SO₃H H H SO₃H H CONH₂ Pentan-2-yl 2 2 2 2 1ab¹³⁴ H H SO₃H SO₃H H H 1ab¹³⁵ Methyl H SO₃H SO₃H H Methyl 1ab¹³⁶ OMe H SO₃H SO₃H H OMe 1ab¹³⁷ H SO₃H H H SO₃H H CONH₂ 2-Ethylhexyl 2 2 2 2 1ab¹³⁸ H H SO₃H SO₃H H H 1ab¹³⁹ Methyl H SO₃H SO₃H H Methyl 1ab¹⁴⁰ OMe H SO₃H SO₃H H OMe 1ab¹⁴¹ H SO₃H H H SO₃H H CONH₂ 2,2-Dimethyl 2 2 2 2 1ab¹⁴² H H SO₃H SO₃H H H propyl 1ab¹⁴³ Methyl H SO₃H SO₃H H Methyl 1ab¹⁴⁴ OMe H SO₃H SO₃H H OMe 1ab¹⁴⁵ H SO₃H H H SO₃H H CONH₂ Phenyl 2 2 2 2 1ab¹⁴⁶ H H SO₃H SO₃H H H 1ab¹⁴⁷ Methyl H SO₃H SO₃H H Methyl 1ab¹⁴⁸ OMe H SO₃H SO₃H H OMe 1ab¹⁴⁹ H SO₃H H H SO₃H H CONH₂ Benzyl 2 2 2 2 1ab¹⁵⁰ H H SO₃H SO₃H H H 1ab¹⁵¹ Methyl H SO₃H SO₃H H Methyl 1ab¹⁵² OMe H SO₃H SO₃H H OMe 1ab¹⁵³ H SO₃H H H SO₃H H CN H 3 4 3 4 1ab¹⁵⁴ H H SO₃H SO₃H H H 1ab¹⁵⁵ Methyl H SO₃H SO₃H H Methyl 1ab¹⁵⁶ OMe H SO₃H SO₃H H OMe 1ab¹⁵⁷ H SO₃H H H SO₃H H CN Ethyl 3 4 3 4 1ab¹⁵⁸ H H SO₃H SO₃H H H 1ab¹⁵⁹ Methyl H SO₃H SO₃H H Methyl 1ab¹⁶⁰ OMe H SO₃H SO₃H H OMe 1ab¹⁶¹ H SO₃H H H SO₃H H CN Propyl 3 4 3 4 1ab¹⁶² H H SO₃H SO₃H H H 1ab¹⁶³ Methyl H SO₃H SO₃H H Methyl 1ab¹⁶⁴ OMe H SO₃H SO₃H H OMe 1ab¹⁶⁵ H SO₃H H H SO₃H H CN Butyl 3 4 3 4 1ab¹⁶⁶ H H SO₃H SO₃H H H 1ab¹⁶⁷ Methyl H SO₃H SO₃H H Methyl 1ab¹⁶⁸ OMe H SO₃H SO₃H H OMe 1ab¹⁶⁹ H SO₃H H H SO₃H H CN Pentyl 3 4 3 4 1ab¹⁷⁰ H H SO₃H SO₃H H H 1ab¹⁷¹ Methyl H SO₃H SO₃H H Methyl 1ab¹⁷² OMe H SO₃H SO₃H H OMe 1ab¹⁷³ H SO₃H H H SO₃H H CN Cyclobutyl 3 4 3 4 1ab¹⁷⁴ H H SO₃H SO₃H H H 1ab¹⁷⁵ Methyl H SO₃H SO₃H H Methyl 1ab¹⁷⁶ OMe H SO₃H SO₃H H OMe 1ab¹⁷⁷ H SO₃H H H SO₃H H CN Cyclopentyl 3 4 3 4 1ab¹⁷⁸ H H SO₃H SO₃H H H 1ab¹⁷⁹ Methyl H SO₃H SO₃H H Methyl 1ab¹⁸⁰ OMe H SO₃H SO₃H H OMe 1ab¹⁸¹ H SO₃H H H SO₃H H CN Isopropyl 3 4 3 4 1ab¹⁸² H H SO₃H SO₃H H H 1ab¹⁸³ Methyl H SO₃H SO₃H H Methyl 1ab¹⁸⁴ OMe H SO₃H SO₃H H OMe 1ab¹⁸⁵ H SO₃H H H SO₃H H CN Sec-butyl 3 4 3 4 1ab¹⁸⁶ H H SO₃H SO₃H H H 1ab¹⁸⁷ Methyl H SO₃H SO₃H H Methyl 1ab¹⁸⁸ OMe H SO₃H SO₃H H OMe 1ab¹⁸⁹ H SO₃H H H SO₃H H CN 2-Methyl butyl 3 4 3 4 1ab¹⁹⁰ H H SO₃H SO₃H H H 1ab¹⁹¹ Methyl H SO₃H SO₃H H Methyl 1ab¹⁹² OMe H SO₃H SO₃H H OMe 1ab¹⁹³ H SO₃H H H SO₃H H CN 1-Ethyl propyl 3 4 3 4 1ab¹⁹⁴ H H SO₃H SO₃H H H 1ab¹⁹⁵ Methyl H SO₃H SO₃H H Methyl 1ab¹⁹⁶ OMe H SO₃H SO₃H H OMe 1ab¹⁹⁷ H SO₃H H H SO₃H H CN 1,2-Dimethyl 3 4 3 4 1ab¹⁹⁸ H H SO₃H SO₃H H H propyl 1ab¹⁹⁹ Methyl H SO₃H SO₃H H Methyl 1ab²⁰⁰ OMe H SO₃H SO₃H H OMe 1ab²⁰¹ H SO₃H H H SO₃H H CN Tert-butyl 3 4 3 4 1ab²⁰² H H SO₃H SO₃H H H 1ab²⁰³ Methyl H SO₃H SO₃H H Methyl 1ab²⁰⁴ OMe H SO₃H SO₃H H OMe 1ab²⁰⁵ H SO₃H H H SO₃H H CN 3-Methyl butyl 3 4 3 4 1ab²⁰⁶ H H SO₃H SO₃H H H 1ab²⁰⁷ Methyl H SO₃H SO₃H H Methyl 1ab²⁰⁸ OMe H SO₃H SO₃H H OMe 1ab²⁰⁹ H SO₃H H H SO₃H H CN Pentan-2-yl 3 4 3 4 1ab²¹⁰ H H SO₃H SO₃H H H 1ab²¹¹ Methyl H SO₃H SO₃H H Methyl 1ab²¹² OMe H SO₃H SO₃H H OMe 1ab²¹³ H SO₃H H H SO₃H H CN 2-Ethylhexyl 3 4 3 4 1ab²¹⁴ H H SO₃H SO₃H H H 1ab²¹⁵ Methyl H SO₃H SO₃H H Methyl 1ab²¹⁶ OMe H SO₃H SO₃H H OMe 1ab²¹⁷ H SO₃H H H SO₃H H CN 2,2-Dimethyl 3 4 3 4 1ab²¹⁸ H H SO₃H SO₃H H H propyl 1ab²¹⁹ Methyl H SO₃H SO₃H H Methyl 1ab²²⁰ OMe H SO₃H SO₃H H OMe 1ab²²¹ H SO₃H H H SO₃H H CN Phenyl 3 4 3 4 1ab²²² H H SO₃H SO₃H H H 1ab²²³ Methyl H SO₃H SO₃H H Methyl 1ab²²⁴ OMe H SO₃H SO₃H H OMe 1ab²²⁵ H SO₃H H H SO₃H H CN Benzyl 3 4 3 4 1ab²²⁶ H H SO₃H SO₃H H H 1ab²²⁷ Methyl H SO₃H SO₃H H Methyl 1ab²²⁸ OMe H SO₃H SO₃H H OMe 1ab²²⁹ H SO₃H H H SO₃H H CONH₂ H 3 4 3 4 1ab²³⁰ H H SO₃H SO₃H H H 1ab²³¹ Methyl H SO₃H SO₃H H Methyl 1ab²³² OMe H SO₃H SO₃H H OMe 1ab²³³ H SO₃H H H SO₃H H CONH₂ Ethyl 3 4 3 4 1ab²³⁴ H H SO₃H SO₃H H H 1ab²³⁵ Methyl H SO₃H SO₃H H Methyl 1ab²³⁶ OMe H SO₃H SO₃H H OMe 1ab²³⁷ H SO₃H H H SO₃H H CONH₂ Propyl 3 4 3 4 1ab²³⁸ H H SO₃H SO₃H H H 1ab²³⁹ Methyl H SO₃H SO₃H H Methyl 1ab²⁴⁰ OMe H SO₃H SO₃H H OMe 1ab²⁴¹ H SO₃H H H SO₃H H CONH₂ Butyl 3 4 3 4 1ab²⁴² H H SO₃H SO₃H H H 1ab²⁴³ Methyl H SO₃H SO₃H H Methyl 1ab²⁴⁴ OMe H SO₃H SO₃H H OMe 1ab²⁴⁵ H SO₃H H H SO₃H H CONH₂ Pentyl 3 4 3 4 1ab²⁴⁶ H H SO₃H SO₃H H H 1ab²⁴⁷ Methyl H SO₃H SO₃H H Methyl 1ab²⁴⁸ OMe H SO₃H SO₃H H OMe 1ab²⁴⁹ H SO₃H H H SO₃H H CONH₂ Cyclobutyl 3 4 3 4 1ab²⁵⁰ H H SO₃H SO₃H H H 1ab²⁵¹ Methyl H SO₃H SO₃H H Methyl 1ab²⁵² OMe H SO₃H SO₃H H OMe 1ab²⁵³ H SO₃H H H SO₃H H CONH₂ Cyclopentyl 3 4 3 4 1ab²⁵⁴ H H SO₃H SO₃H H H 1ab²⁵⁵ Methyl H SO₃H SO₃H H Methyl 1ab²⁵⁶ OMe H SO₃H SO₃H H OMe 1ab²⁵⁷ H SO₃H H H SO₃H H CONH₂ Isopropyl 3 4 3 4 1ab²⁵⁸ H H SO₃H SO₃H H H 1ab²⁵⁹ Methyl H SO₃H SO₃H H Methyl 1ab²⁶⁰ OMe H SO₃H SO₃H H OMe 1ab²⁶¹ H SO₃H H H SO₃H H CONH₂ Sec-butyl 3 4 3 4 1ab²⁶² H H SO₃H SO₃H H H 1ab²⁶³ Methyl H SO₃H SO₃H H Methyl 1ab²⁶⁴ OMe H SO₃H SO₃H H OMe 1ab²⁶⁵ H SO₃H H H SO₃H H CONH₂ 2-Methyl butyl 3 4 3 4 1ab²⁶⁶ H H SO₃H SO₃H H H 1ab²⁶⁷ Methyl H SO₃H SO₃H H Methyl 1ab²⁶⁸ OMe H SO₃H SO₃H H OMe 1ab²⁶⁹ H SO₃H H H SO₃H H CONH₂ 1-Ethyl propyl 3 4 3 4 1ab²⁷⁰ H H SO₃H SO₃H H H 1ab²⁷¹ Methyl H SO₃H SO₃H H Methyl 1ab²⁷² OMe H SO₃H SO₃H H OMe 1ab²⁷³ H SO₃H H H SO₃H H CONH₂ 1,2-Dimethyl 3 4 3 4 1ab²⁷⁴ H H SO₃H SO₃H H H propyl 1ab²⁷⁵ Methyl H SO₃H SO₃H H Methyl 1ab²⁷⁶ OMe H SO₃H SO₃H H OMe 1ab²⁷⁷ H SO₃H H H SO₃H H CONH₂ Tert-butyl 3 4 3 4 1ab²⁷⁸ H H SO₃H SO₃H H H 1ab²⁷⁹ Methyl H SO₃H SO₃H H Methyl 1ab²⁸⁰ OMe H SO₃H SO₃H H OMe 1ab²⁸¹ H SO₃H H H SO₃H H CONH₂ 3-Methyl butyl 3 4 3 4 1ab²⁸² H H SO₃H SO₃H H H 1ab²⁸³ Methyl H SO₃H SO₃H H Methyl 1ab²⁸⁴ OMe H SO₃H SO₃H H OMe 1ab²⁸⁵ H SO₃H H H SO₃H H CONH₂ Pentan-2-yl 3 4 3 4 1ab²⁸⁶ H H SO₃H SO₃H H H 1ab²⁸⁷ Methyl H SO₃H SO₃H H Methyl 1ab²⁸⁸ OMe H SO₃H SO₃H H OMe 1ab²⁸⁹ H SO₃H H H SO₃H H CONH₂ 2-Ethylhexyl 3 4 3 4 1ab²⁹⁰ H H SO₃H SO₃H H H 1ab²⁹¹ Methyl H SO₃H SO₃H H Methyl 1ab²⁹² OMe H SO₃H SO₃H H OMe 1ab²⁹³ H SO₃H H H SO₃H H CONH₂ 2,2-Dimethyl 3 4 3 4 1ab²⁹⁴ H H SO₃H SO₃H H H propyl 1ab²⁹⁵ Methyl H SO₃H SO₃H H Methyl 1ab²⁹⁶ OMe H SO₃H SO₃H H OMe 1ab²⁹⁷ H SO₃H H H SO₃H H CONH₂ Phenyl 3 4 3 4 1ab²⁹⁸ H H SO₃H SO₃H H H 1ab²⁹⁹ Methyl H SO₃H SO₃H H Methyl 1ab³⁰⁰ OMe H SO₃H SO₃H H OMe 1ab³⁰¹ H SO₃H H H SO₃H H CONH₂ Benzyl 3 4 3 4 1ab³⁰² H H SO₃H SO₃H H H 1ab³⁰³ Methyl H SO₃H SO₃H H Methyl 1ab³⁰⁴ OMe H SO₃H SO₃H H OMe 1ab³⁰⁵ H SO₃H H H SO₃H H CN H 3 3 3 3 1ab³⁰⁶ H H SO₃H SO₃H H H 1ab³⁰⁷ Methyl H SO₃H SO₃H H Methyl 1ab³⁰⁸ OMe H SO₃H SO₃H H OMe 1ab³⁰⁹ H SO₃H H H SO₃H H CN Ethyl 3 3 3 3 1ab³¹⁰ H H SO₃H SO₃H H H 1ab³¹¹ Methyl H SO₃H SO₃H H Methyl 1ab³¹² OMe H SO₃H SO₃H H OMe 1ab³¹³ H SO₃H H H SO₃H H CN Propyl 3 3 3 3 1ab³¹⁴ H H SO₃H SO₃H H H 1ab³¹⁵ Methyl H SO₃H SO₃H H Methyl 1ab³¹⁶ OMe H SO₃H SO₃H H OMe 1ab³¹⁷ H SO₃H H H SO₃H H CN Butyl 3 3 3 3 1ab³¹⁸ H H SO₃H SO₃H H H 1ab³¹⁹ Methyl H SO₃H SO₃H H Methyl 1ab³²⁰ OMe H SO₃H SO₃H H OMe 1ab³²¹ H SO₃H H H SO₃H H CN Pentyl 3 3 3 3 1ab³²² H H SO₃H SO₃H H H 1ab³²³ Methyl H SO₃H SO₃H H Methyl 1ab³²⁴ OMe H SO₃H SO₃H H OMe 1ab³²⁵ H SO₃H H H SO₃H H CN Cyclobutyl 3 3 3 3 1ab³²⁶ H H SO₃H SO₃H H H 1ab³²⁷ Methyl H SO₃H SO₃H H Methyl 1ab³²⁸ OMe H SO₃H SO₃H H OMe 1ab³²⁹ H SO₃H H H SO₃H H CN Cyclopentyl 3 3 3 3 1ab³³⁰ H H SO₃H SO₃H H H 1ab³³¹ Methyl H SO₃H SO₃H H Methyl 1ab³³² OMe H SO₃H SO₃H H OMe 1ab³³³ H SO₃H H H SO₃H H CN Isopropyl 3 3 3 3 1ab³³⁴ H H SO₃H SO₃H H H 1ab³³⁵ Methyl H SO₃H SO₃H H Methyl 1ab³³⁶ OMe H SO₃H SO₃H H OMe 1ab³³⁷ H SO₃H H H SO₃H H CN Sec-butyl 3 3 3 3 1ab³³⁸ H H SO₃H SO₃H H H 1ab³³⁹ Methyl H SO₃H SO₃H H Methyl 1ab³⁴⁰ OMe H SO₃H SO₃H H OMe 1ab³⁴¹ H SO₃H H H SO₃H H CN 2-Methyl butyl 3 3 3 3 1ab³⁴² H H SO₃H SO₃H H H 1ab³⁴³ Methyl H SO₃H SO₃H H Methyl 1ab³⁴⁴ OMe H SO₃H SO₃H H OMe 1ab³⁴⁵ H SO₃H H H SO₃H H CN 1-Ethyl propyl 3 3 3 3 1ab³⁴⁶ H H SO₃H SO₃H H H 1ab³⁴⁷ Methyl H SO₃H SO₃H H Methyl 1ab³⁴⁸ OMe H SO₃H SO₃H H OMe 1ab³⁴⁹ H SO₃H H H SO₃H H CN 1,2-Dimethyl 3 3 3 3 1ab³⁵⁰ H H SO₃H SO₃H H H propyl 1ab³⁵¹ Methyl H SO₃H SO₃H H Methyl 1ab³⁵² OMe H SO₃H SO₃H H OMe 1ab³⁵³ H SO₃H H H SO₃H H CN Tert-butyl 3 3 3 3 1ab³⁵⁴ H H SO₃H SO₃H H H 1ab³⁵⁵ Methyl H SO₃H SO₃H H Methyl 1ab³⁵⁶ OMe H SO₃H SO₃H H OMe 1ab³⁵⁷ H SO₃H H H SO₃H H CN 3-Methyl butyl 3 3 3 3 1ab³⁵⁸ H H SO₃H SO₃H H H 1ab³⁵⁹ Methyl H SO₃H SO₃H H Methyl 1ab³⁶⁰ OMe H SO₃H SO₃H H OMe 1ab³⁶¹ H SO₃H H H SO₃H H CN Pentan-2-yl 3 3 3 3 1ab³⁶² H H SO₃H SO₃H H H 1ab³⁶³ Methyl H SO₃H SO₃H H Methyl 1ab³⁶⁴ OMe H SO₃H SO₃H H OMe 1ab³⁶⁵ H SO₃H H H SO₃H H CN 2-Ethylhexyl 3 3 3 3 1ab³⁶⁶ H H SO₃H SO₃H H H 1ab³⁶⁷ Methyl H SO₃H SO₃H H Methyl 1ab³⁶⁸ OMe H SO₃H SO₃H H OMe 1ab³⁶⁹ H SO₃H H H SO₃H H CN 2,2-Dimethyl 3 3 3 3 1ab³⁷⁰ H H SO₃H SO₃H H H propyl 1ab³⁷¹ Methyl H SO₃H SO₃H H Methyl 1ab³⁷² OMe H SO₃H SO₃H H OMe 1ab³⁷³ H SO₃H H H SO₃H H CN Phenyl 3 3 3 3 1ab³⁷⁴ H H SO₃H SO₃H H H 1ab³⁷⁵ Methyl H SO₃H SO₃H H Methyl 1ab³⁷⁶ OMe H SO₃H SO₃H H OMe 1ab³⁷⁷ H SO₃H H H SO₃H H CN Benzyl 3 3 3 3 1ab³⁷⁸ H H SO₃H SO₃H H H 1ab³⁷⁹ Methyl H SO₃H SO₃H H Methyl 1ab³⁸⁰ OMe H SO₃H SO₃H H OMe 1ab³⁸¹ H SO₃H H H SO₃H H CONH₂ H 3 3 3 3 1ab³⁸² H H SO₃H SO₃H H H 1ab³⁸³ Methyl H SO₃H SO₃H H Methyl 1ab³⁸⁴ OMe H SO₃H SO₃H H OMe 1ab³⁸⁵ H SO₃H H H SO₃H H CONH₂ Ethyl 3 3 3 3 1ab³⁸⁶ H H SO₃H SO₃H H H 1ab³⁸⁷ Methyl H SO₃H SO₃H H Methyl 1ab³⁸⁸ OMe H SO₃H SO₃H H OMe 1ab³⁸⁹ H SO₃H H H SO₃H H CONH₂ Propyl 3 3 3 3 1ab³⁹⁰ H H SO₃H SO₃H H H 1ab³⁹¹ Methyl H SO₃H SO₃H H Methyl 1ab³⁹² OMe H SO₃H SO₃H H OMe 1ab³⁹³ H SO₃H H H SO₃H H CONH₂ Butyl 3 3 3 3 1ab³⁹⁴ H H SO₃H SO₃H H H 1ab³⁹⁵ Methyl H SO₃H SO₃H H Methyl 1ab³⁹⁶ OMe H SO₃H SO₃H H OMe 1ab³⁹⁷ H SO₃H H H SO₃H H CONH₂ Pentyl 3 3 3 3 1ab³⁹⁸ H H SO₃H SO₃H H H 1ab³⁹⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁰⁰ OMe H SO₃H SO₃H H OMe 1ab⁴⁰¹ H SO₃H H H SO₃H H CONH₂ Cyclobutyl 3 3 3 3 1ab⁴⁰² H H SO₃H SO₃H H H 1ab⁴⁰³ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁰⁴ OMe H SO₃H SO₃H H OMe 1ab⁴⁰⁵ H SO₃H H H SO₃H H CONH₂ Cyclopentyl 3 3 3 3 1ab⁴⁰⁶ H H SO₃H SO₃H H H 1ab⁴⁰⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁰⁸ OMe H SO₃H SO₃H H OMe 1ab⁴⁰⁹ H SO₃H H H SO₃H H CONH₂ Isopropyl 3 3 3 3 1ab⁴¹⁰ H H SO₃H SO₃H H H 1ab⁴¹¹ Methyl H SO₃H SO₃H H Methyl 1ab⁴¹² OMe H SO₃H SO₃H H OMe 1ab⁴¹³ H SO₃H H H SO₃H H CONH₂ Sec-butyl 3 3 3 3 1ab⁴¹⁴ H H SO₃H SO₃H H H 1ab⁴¹⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁴¹⁶ OMe H SO₃H SO₃H H OMe 1ab⁴¹⁷ H SO₃H H H SO₃H H CONH₂ 2-Methyl butyl 3 3 3 3 1ab⁴¹⁸ H H SO₃H SO₃H H H 1ab⁴¹⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁴²⁰ OMe H SO₃H SO₃H H OMe 1ab⁴²¹ H SO₃H H H SO₃H H CONH₂ 1-Ethyl propyl 3 3 3 3 1ab⁴²² H H SO₃H SO₃H H H 1ab⁴²³ Methyl H SO₃H SO₃H H Methyl 1ab⁴²⁴ OMe H SO₃H SO₃H H OMe 1ab⁴²⁵ H SO₃H H H SO₃H H CONH₂ 1,2-Dimethyl 3 3 3 3 1ab⁴²⁶ H H SO₃H SO₃H H H propyl 1ab⁴²⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁴²⁸ OMe H SO₃H SO₃H H OMe 1ab⁴²⁹ H SO₃H H H SO₃H H CONH₂ Tert-butyl 3 3 3 3 1ab⁴³⁰ H H SO₃H SO₃H H H 1ab⁴³¹ Methyl H SO₃H SO₃H H Methyl 1ab⁴³² OMe H SO₃H SO₃H H OMe 1ab⁴³³ H SO₃H H H SO₃H H CONH₂ 3-Methyl butyl 3 3 3 3 1ab⁴³⁴ H H SO₃H SO₃H H H 1ab⁴³⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁴³⁶ OMe H SO₃H SO₃H H OMe 1ab⁴³⁷ H SO₃H H H SO₃H H CONH₂ Pentan-2-yl 3 3 3 3 1ab⁴³⁸ H H SO₃H SO₃H H H 1ab⁴³⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁴⁰ OMe H SO₃H SO₃H H OMe 1ab⁴⁴¹ H SO₃H H H SO₃H H CONH₂ 2-Ethylhexyl 3 3 3 3 1ab⁴⁴² H H SO₃H SO₃H H H 1ab⁴⁴³ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁴⁴ OMe H SO₃H SO₃H H OMe 1ab⁴⁴⁵ H SO₃H H H SO₃H H CONH₂ 2,2-Dimethyl 3 3 3 3 1ab⁴⁴⁶ H H SO₃H SO₃H H H propyl 1ab⁴⁴⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁴⁸ OMe H SO₃H SO₃H H OMe 1ab⁴⁴⁹ H SO₃H H H SO₃H H CONH₂ Phenyl 3 3 3 3 1ab⁴⁵⁰ H H SO₃H SO₃H H H 1ab⁴⁵¹ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁵² OMe H SO₃H SO₃H H OMe 1ab⁴⁵³ H SO₃H H H SO₃H H CONH₂ Benzyl 3 3 3 3 1ab⁴⁵⁴ H H SO₃H SO₃H H H 1ab⁴⁵⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁵⁶ OMe H SO₃H SO₃H H OMe 1ab⁴⁵⁷ H SO₃H H H SO₃H H CN 2-Methoxy ethyl 2 2 2 2 1ab⁴⁵⁸ H H SO₃H SO₃H H H 1ab⁴⁵⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁶⁰ OMe H SO₃H SO₃H H OMe 1ab⁴⁶¹ H SO₃H H H SO₃H H CN 3-Methoxy 2 2 2 2 1ab⁴⁶² H H SO₃H SO₃H H H propyl 1ab⁴⁶³ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁶⁴ OMe H SO₃H SO₃H H OMe 1ab⁴⁶⁵ H SO₃H H H SO₃H H CN 2-Hydroxy ethyl 2 2 2 2 1ab⁴⁶⁶ H H SO₃H SO₃H H H 1ab⁴⁶⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁶⁸ OMe H SO₃H SO₃H H OMe 1ab⁴⁶⁹ H SO₃H H H SO₃H H CN 2-Fluoro ethyl 2 2 2 2 1ab⁴⁷⁰ H H SO₃H SO₃H H H 1ab⁴⁷¹ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁷² OMe H SO₃H SO₃H H OMe 1ab⁴⁷³ H SO₃H H H SO₃H H CN 2-Chloro ethyl 2 2 2 2 1ab⁴⁷⁴ H H SO₃H SO₃H H H 1ab⁴⁷⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁷⁶ OMe H SO₃H SO₃H H OMe 1ab⁴⁷⁷ H SO₃H H H SO₃H H CN 3-Chloro propyl 2 2 2 2 1ab⁴⁷⁸ H H SO₃H SO₃H H H 1ab⁴⁷⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁴⁸⁰ OMe H SO₃H SO₃H H OMe 1ab⁴⁸¹ H SO₃H H H SO₃H H CN 2-(2-Hydroxy- 2 2 2 2 1ab⁴⁸² H H SO₃H SO₃H H H ethyl sulfanyl)- 1ab⁴⁸³ Methyl H SO₃H SO₃H H Methyl ethyl 1ab⁴⁸⁴ OMe H SO₃H SO₃H H OMe 1ab⁴⁸⁵ H SO₃H H H SO₃H H CN 2-(2-tert-Butyl 2 2 2 2 1ab⁴⁸⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1ab⁴⁸⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1ab⁴⁸⁸ OMe H SO₃H SO₃H H OMe 1ab⁴⁸⁹ H SO₃H H H SO₃H H CN 3-(4-Hydroxy 2 2 2 2 1ab⁴⁹⁰ H H SO₃H SO₃H H H butoxy) 1ab⁴⁹¹ Methyl H SO₃H SO₃H H Methyl propyl 1ab⁴⁹² OMe H SO₃H SO₃H H OMe 1ab⁴⁹³ H SO3H H H SO3H H CN 2-(2-Hydroxy 2 2 2 2 1ab⁴⁹⁴ H H SO3H SO3H H H ethoxy)ethyl 1ab⁴⁹⁵ Methyl H SO3H SO3H H Methyl 1ab⁴⁹⁶ OMe H SO3H SO3H H OMe 1ab⁴⁹⁷ H SO₃H H H SO₃H H CN 4-(2-Hydroxy- 2 2 2 2 1ab⁴⁹⁸ H H SO₃H SO₃H H H ethane 1ab⁴⁹⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1ab⁵⁰⁰ OMe H SO₃H SO₃H H OMe 1ab⁵⁰¹ H SO₃H H H SO₃H H CN 3-(2-Phenoxy- 2 2 2 2 1ab⁵⁰² H H SO₃H SO₃H H H ethoxy)-propyl 1ab⁵⁰³ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁰⁴ OMe H SO₃H SO₃H H OMe 1ab⁵⁰⁵ H SO₃H H H SO₃H H CN 3-Isopropoxy- 2 2 2 2 1ab⁵⁰⁶ H H SO₃H SO₃H H H propyl 1ab⁵⁰⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁰⁸ OMe H SO₃H SO₃H H OMe 1ab⁵⁰⁹ H SO₃H H H SO₃H H CN 3-Ethoxy-propyl 2 2 2 2 1ab⁵¹⁰ H H SO₃H SO₃H H H 1ab⁵¹¹ Methyl H SO₃H SO₃H H Methyl 1ab⁵¹² OMe H SO₃H SO₃H H OMe 1ab⁵¹³ H SO₃H H H SO₃H H CN 3-Ethoxybutyl 2 2 2 2 1ab⁵¹⁴ H H SO₃H SO₃H H H 1ab⁵¹⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁵¹⁶ OMe H SO₃H SO₃H H OMe 1ab⁵¹⁷ H SO₃H H H SO₃H H CONH₂ 2-Methoxy ethyl 2 2 2 2 1ab⁵¹⁸ H H SO₃H SO₃H H H 1ab⁵¹⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁵²⁰ OMe H SO₃H SO₃H H OMe 1ab⁵²¹ H SO₃H H H SO₃H H CONH₂ 3-Methoxy 2 2 2 2 1ab⁵²² H H SO₃H SO₃H H H propyl 1ab⁵²³ Methyl H SO₃H SO₃H H Methyl 1ab⁵²⁴ OMe H SO₃H SO₃H H OMe 1ab⁵²⁵ H SO₃H H H SO₃H H CONH₂ 2-Hydroxyethyl 2 2 2 2 1ab⁵²⁶ H H SO₃H SO₃H H H 1ab⁵²⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁵²⁸ OMe H SO₃H SO₃H H OMe 1ab⁵²⁹ H SO₃H H H SO₃H H CONH₂ 2-Fluoro ethyl 2 2 2 2 1ab⁵³⁰ H H SO₃H SO₃H H H 1ab⁵³¹ Methyl H SO₃H SO₃H H Methyl 1ab⁵³² OMe H SO₃H SO₃H H OMe 1ab⁵³³ H SO₃H H H SO₃H H CONH₂ 2-Chloro ethyl 2 2 2 2 1ab⁵³⁴ H H SO₃H SO₃H H H 1ab⁵³⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁵³⁶ OMe H SO₃H SO₃H H OMe 1ab⁵³⁷ H SO₃H H H SO₃H H CONH₂ 3-Chloro propyl 2 2 2 2 1ab⁵³⁸ H H SO₃H SO₃H H H 1ab⁵³⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁴⁰ OMe H SO₃H SO₃H H OMe 1ab⁵⁴¹ H SO₃H H H SO₃H H CONH₂ 2-(2-Hydroxy- 2 2 2 2 1ab⁵⁴² H H SO₃H SO₃H H H ethyl sulfanyl)- 1ab⁵⁴³ Methyl H SO₃H SO₃H H Methyl ethyl 1ab⁵⁴⁴ OMe H SO₃H SO₃H H OMe 1ab⁵⁴⁵ H SO₃H H H SO₃H H CONH₂ 2-(2-tert-Butyl 2 2 2 2 1ab⁵⁴⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1ab⁵⁴⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1ab⁵⁴⁸ OMe H SO₃H SO₃H H OMe 1ab⁵⁴⁹ H SO₃H H H SO₃H H CONH₂ 3-(4-Hydroxy 2 2 2 2 1ab⁵⁵⁰ H H SO₃H SO₃H H H butoxy) 1ab⁵⁵¹ Methyl H SO₃H SO₃H H Methyl propyl 1ab⁵⁵² OMe H SO₃H SO₃H H OMe 1ab⁵⁵³ H SO3H H H SO3H H CONH₂ 2-(2-Hydroxy 2 2 2 2 1ab⁵⁵⁴ H H SO3H SO3H H H ethoxy)ethyl 1ab⁵⁵⁵ Methyl H SO3H SO3H H Methyl 1ab⁵⁵⁶ OMe H SO3H SO3H H OMe 1ab⁵⁵⁷ H SO₃H H H SO₃H H CONH₂ 4-(2-Hydroxy- 2 2 2 2 1ab⁵⁵⁸ H H SO₃H SO₃H H H ethane 1ab⁵⁵⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1ab⁵⁶⁰ OMe H SO₃H SO₃H H OMe 1ab⁵⁶¹ H SO₃H H H SO₃H H CONH₂ 3-(2-Phenoxy- 2 2 2 2 1ab⁵⁶² H H SO₃H SO₃H H H ethoxy)-propyl 1ab⁵⁶³ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁶⁴ OMe H SO₃H SO₃H H OMe 1ab⁵⁶⁵ H SO₃H H H SO₃H H CONH₂ 3-Isopropoxy- 2 2 2 2 1ab⁵⁶⁶ H H SO₃H SO₃H H H propyl 1ab⁵⁶⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁶⁸ OMe H SO₃H SO₃H H OMe 1ab⁵⁶⁹ H SO₃H H H SO₃H H CONH₂ 3-Ethoxy propyl 2 2 2 2 1ab⁵⁷⁰ H H SO₃H SO₃H H H 1ab⁵⁷¹ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁷² OMe H SO₃H SO₃H H OMe 1ab⁵⁷³ H SO₃H H H SO₃H H CONH₂ 4-Ethoxy butyl 2 2 2 2 1ab⁵⁷⁴ H H SO₃H SO₃H H H 1ab⁵⁷⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁷⁶ OMe H SO₃H SO₃H H OMe 1ab⁵⁷⁷ H SO₃H H H SO₃H H CN 2-Methoxy ethyl 3 4 3 4 1ab⁵⁷⁸ H H SO₃H SO₃H H H 1ab⁵⁷⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁸⁰ OMe H SO₃H SO₃H H OMe 1ab⁵⁸¹ H SO₃H H H SO₃H H CN 3-Methoxy 3 4 3 4 1ab⁵⁸² H H SO₃H SO₃H H H propyl 1ab⁵⁸³ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁸⁴ OMe H SO₃H SO₃H H OMe 1ab⁵⁸⁵ H SO₃H H H SO₃H H CN 2-Hydroxyethyl 3 4 3 4 1ab⁵⁸⁶ H H SO₃H SO₃H H H 1ab⁵⁸⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁸⁸ OMe H SO₃H SO₃H H OMe 1ab⁵⁸⁹ H SO₃H H H SO₃H H CN 2-Fluoro ethyl 3 4 3 4 1ab⁵⁹⁰ H H SO₃H SO₃H H H 1ab⁵⁹¹ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁹² OMe H SO₃H SO₃H H OMe 1ab⁵⁹³ H SO₃H H H SO₃H H CN 2-Chloro ethyl 3 4 3 4 1ab⁵⁹⁴ H H SO₃H SO₃H H H 1ab⁵⁹⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁵⁹⁶ OMe H SO₃H SO₃H H OMe 1ab⁵⁹⁷ H SO₃H H H SO₃H H CN 3-Chloro propyl 3 4 3 4 1ab⁵⁹⁸ H H SO₃H SO₃H H H 1ab⁵⁹⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁰⁰ OMe H SO₃H SO₃H H OMe 1ab⁶⁰¹ H SO₃H H H SO₃H H CN 2-(2-Hydroxy- 3 4 3 4 1ab⁶⁰² H H SO₃H SO₃H H H ethyl sulfanyl)- 1ab⁶⁰³ Methyl H SO₃H SO₃H H Methyl ethyl 1ab⁶⁰⁴ OMe H SO₃H SO₃H H OMe 1ab⁶⁰⁵ H SO₃H H H SO₃H H CN 2-(2-tert-Butyl 3 4 3 4 1ab⁶⁰⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1ab⁶⁰⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1ab⁶⁰⁸ OMe H SO₃H SO₃H H OMe 1ab⁶⁰⁹ H SO₃H H H SO₃H H CN 3-(4-Hydroxy 3 4 3 4 1ab⁶¹⁰ H H SO₃H SO₃H H H butoxy) 1ab⁶¹¹ Methyl H SO₃H SO₃H H Methyl propyl 1ab⁶¹² OMe H SO₃H SO₃H H OMe 1ab⁶¹³ H SO3H H H SO3H H CN 2-(2-Hydroxy 3 4 3 4 1ab⁶¹⁴ H H SO3H SO3H H H ethoxy)ethyl 1ab⁶¹⁵ Methyl H SO3H SO3H H Methyl 1ab⁶¹⁶ OMe H SO3H SO3H H OMe 1ab⁶¹⁷ H SO₃H H H SO₃H H CN 4-(2-Hydroxy- 3 4 3 4 1ab⁶¹⁸ H H SO₃H SO₃H H H ethane 1ab⁶¹⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1ab⁶²⁰ OMe H SO₃H SO₃H H OMe 1ab⁶²¹ H SO₃H H H SO₃H H CN 3-(2-Phenoxy- 3 4 3 4 1ab⁶²² H H SO₃H SO₃H H H ethoxy)-propyl 1ab⁶²³ Methyl H SO₃H SO₃H H Methyl 1ab⁶²⁴ OMe H SO₃H SO₃H H OMe 1ab⁶²⁵ H SO₃H H H SO₃H H CN 3-Isopropoxy- 3 4 3 4 1ab⁶²⁶ H H SO₃H SO₃H H H propyl 1ab⁶²⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁶²⁸ OMe H SO₃H SO₃H H OMe 1ab⁶²⁹ H SO₃H H H SO₃H H CN 3-Ethoxy propyl 3 4 3 4 1ab⁶³⁰ H H SO₃H SO₃H H H 1ab⁶³¹ Methyl H SO₃H SO₃H H Methyl 1ab⁶³² OMe H SO₃H SO₃H H OMe 1ab⁶³³ H SO₃H H H SO₃H H CN 4-Ethoxy butyl 3 4 3 4 1ab⁶³⁴ H H SO₃H SO₃H H H 1ab⁶³⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁶³⁶ OMe H SO₃H SO₃H H OMe 1ab⁶³⁷ H SO₃H H H SO₃H H CONH₂ 2-Methoxy ethyl 3 4 3 4 1ab⁶³⁸ H H SO₃H SO₃H H H 1ab⁶³⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁴⁰ OMe H SO₃H SO₃H H OMe 1ab⁶⁴¹ H SO₃H H H SO₃H H CONH₂ 3-Methoxy 3 4 3 4 1ab⁶⁴² H H SO₃H SO₃H H H propyl 1ab⁶⁴³ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁴⁴ OMe H SO₃H SO₃H H OMe 1ab⁶⁴⁵ H SO₃H H H SO₃H H CONH₂ 2-Hydroxyethyl 3 4 3 4 1ab⁶⁴⁶ H H SO₃H SO₃H H H 1ab⁶⁴⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁴⁸ OMe H SO₃H SO₃H H OMe 1ab⁶⁴⁹ H SO₃H H H SO₃H H CONH₂ 2-Fluoro ethyl 3 4 3 4 1ab⁶⁵⁰ H H SO₃H SO₃H H H 1ab⁶⁵¹ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁵² OMe H SO₃H SO₃H H OMe 1ab⁶⁵³ H SO₃H H H SO₃H H CONH₂ 2-Chloro ethyl 3 4 3 4 1ab⁶⁵⁴ H H SO₃H SO₃H H H 1ab⁶⁵⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁵⁶ OMe H SO₃H SO₃H H OMe 1ab⁶⁵⁷ H SO₃H H H SO₃H H CONH₂ 3-Chloro propyl 3 4 3 4 1ab⁶⁵⁸ H H SO₃H SO₃H H H 1ab⁶⁵⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁶⁰ OMe H SO₃H SO₃H H OMe 1ab⁶⁶¹ H SO₃H H H SO₃H H CONH₂ 2-(2-Hydroxy- 3 4 3 4 1ab⁶⁶² H H SO₃H SO₃H H H ethyl sulfanyl)- 1ab⁶⁶³ Methyl H SO₃H SO₃H H Methyl ethyl 1ab⁶⁶⁴ OMe H SO₃H SO₃H H OMe 1ab⁶⁶⁵ H SO₃H H H SO₃H H CONH₂ 2-(2-tert-Butyl 3 4 3 4 1ab⁶⁶⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1ab⁶⁶⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1ab⁶⁶⁸ OMe H SO₃H SO₃H H OMe 1ab⁶⁶⁹ H SO₃H H H SO₃H H CONH₂ 3-(4-Hydroxy 3 4 3 4 1ab⁶⁷⁰ H H SO₃H SO₃H H H butoxy) 1ab⁶⁷¹ Methyl H SO₃H SO₃H H Methyl propyl 1ab⁶⁷² OMe H SO₃H SO₃H H OMe 1ab⁶⁷³ H SO3H H H SO3H H CONH₂ 2-(2-Hydroxy 3 4 3 4 1ab⁶⁷⁴ H H SO3H SO3H H H ethoxy)ethyl 1ab⁶⁷⁵ Methyl H SO3H SO3H H Methyl 1ab⁶⁷⁶ OMe H SO3H SO3H H OMe 1ab⁶⁷⁷ H SO₃H H H SO₃H H CONH₂ 4-(2-Hydroxy- 3 4 3 4 1ab⁶⁷⁸ H H SO₃H SO₃H H H ethane 1ab⁶⁷⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1ab⁶⁸⁰ OMe H SO₃H SO₃H H OMe 1ab⁶⁸¹ H SO₃H H H SO₃H H CONH₂ 3-(2-Phenoxy- 3 4 3 4 1ab⁶⁸² H H SO₃H SO₃H H H ethoxy)-propyl 1ab⁶⁸³ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁸⁴ OMe H SO₃H SO₃H H OMe 1ab⁶⁸⁵ H SO₃H H H SO₃H H CONH₂ 3-Isopropoxy- 3 4 3 4 1ab⁶⁸⁶ H H SO₃H SO₃H H H propyl 1ab⁶⁸⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁸⁸ OMe H SO₃H SO₃H H OMe 1ab⁶⁸⁹ H SO₃H H H SO₃H H CONH₂ 3-Ethoxy propyl 3 4 3 4 1ab⁶⁹⁰ H H SO₃H SO₃H H H 1ab⁶⁹¹ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁹² OMe H SO₃H SO₃H H OMe 1ab⁶⁹³ H SO₃H H H SO₃H H CONH₂ 4-Ethoxy butyl 3 4 3 4 1ab⁶⁹⁴ H H SO₃H SO₃H H H 1ab⁶⁹⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁶⁹⁶ OMe H SO₃H SO₃H H OMe 1ab⁶⁹⁷ H SO₃H H H SO₃H H CN 2-Methoxy ethyl 3 3 3 3 1ab⁶⁹⁸ H H SO₃H SO₃H H H 1ab⁶⁹⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁰⁰ OMe H SO₃H SO₃H H OMe 1ab⁷⁰¹ H SO₃H H H SO₃H H CN 3-Methoxy 3 3 3 3 1ab⁷⁰² H H SO₃H SO₃H H H propyl 1ab⁷⁰³ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁰⁴ OMe H SO₃H SO₃H H OMe 1ab⁷⁰⁵ H SO₃H H H SO₃H H CN 2-Hydroxy ethyl 3 3 3 3 1ab⁷⁰⁶ H H SO₃H SO₃H H H 1ab⁷⁰⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁰⁸ OMe H SO₃H SO₃H H OMe 1ab⁷⁰⁹ H SO₃H H H SO₃H H CN 2-Fluoro ethyl 3 3 3 3 1ab⁷¹⁰ H H SO₃H SO₃H H H 1ab⁷¹¹ Methyl H SO₃H SO₃H H Methyl 1ab⁷¹² OMe H SO₃H SO₃H H OMe 1ab⁷¹³ H SO₃H H H SO₃H H CN 2-Chloro ethyl 3 3 3 3 1ab⁷¹⁴ H H SO₃H SO₃H H H 1ab⁷¹⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁷¹⁶ OMe H SO₃H SO₃H H OMe 1ab⁷¹⁷ H SO₃H H H SO₃H H CN 3-Chloro propyl 3 3 3 3 1ab⁷¹⁸ H H SO₃H SO₃H H H 1ab⁷¹⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁷²⁰ OMe H SO₃H SO₃H H OMe 1ab⁷²¹ H SO₃H H H SO₃H H CN 2-(2-Hydroxy- 3 3 3 3 1ab⁷²² H H SO₃H SO₃H H H ethyl sulfanyl)- 1ab⁷²³ Methyl H SO₃H SO₃H H Methyl ethyl 1ab⁷²⁴ OMe H SO₃H SO₃H H OMe 1ab⁷²⁵ H SO₃H H H SO₃H H CN 2-(2-tert-Butyl 3 3 3 3 1ab⁷²⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1ab⁷²⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1ab⁷²⁸ OMe H SO₃H SO₃H H OMe 1ab⁷²⁹ H SO₃H H H SO₃H H CN 3-(4-Hydroxy 3 3 3 3 1ab⁷³⁰ H H SO₃H SO₃H H H butoxy) 1ab⁷³¹ Methyl H SO₃H SO₃H H Methyl propyl 1ab⁷³² OMe H SO₃H SO₃H H OMe 1ab⁷³³ H SO3H H H SO3H H CN 2-(2-Hydroxy 3 3 3 3 1ab⁷³⁴ H H SO3H SO3H H H ethoxy)ethyl 1ab⁷³⁵ Methyl H SO3H SO3H H Methyl 1ab⁷³⁶ OMe H SO3H SO3H H OMe 1ab⁷³⁷ H SO₃H H H SO₃H H CN 4-(2-Hydroxy- 3 3 3 3 1ab⁷³⁸ H H SO₃H SO₃H H H ethane 1ab⁷³⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1ab⁷⁴⁰ OMe H SO₃H SO₃H H OMe 1ab⁷⁴¹ H SO₃H H H SO₃H H CN 3-(2-Phenoxy- 3 3 3 3 1ab⁷⁴² H H SO₃H SO₃H H H ethoxy)-propyl 1ab⁷⁴³ H SO₃H SO₃H H Methyl 1ab⁷⁴⁴ OMe H SO₃H SO₃H H OMe 1ab⁷⁴⁵ H SO₃H H H SO₃H H CN 3-Isopropoxy- 3 3 3 3 1ab⁷⁴⁶ H H SO₃H SO₃H H H propyl 1ab⁷⁴⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁴⁸ OMe H SO₃H SO₃H H OMe 1ab⁷⁴⁹ H SO₃H H H SO₃H H CN 3-Ethoxypropyl 3 3 3 3 1ab⁷⁵⁰ H H SO₃H SO₃H H H 1ab⁷⁵¹ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁵² OMe H SO₃H SO₃H H OMe 1ab⁷⁵³ H SO₃H H H SO₃H H CN 3-Ethoxybutyl 3 3 3 3 1ab⁷⁵⁴ H H SO₃H SO₃H H H 1ab⁷⁵⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁵⁶ OMe H SO₃H SO₃H H OMe 1ab⁷⁵⁷ H SO₃H H H SO₃H H CONH₂ 2-Methoxyethyl 3 3 3 3 1ab⁷⁵⁸ H H SO₃H SO₃H H H 1ab⁷⁵⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁶⁰ OMe H SO₃H SO₃H H OMe 1ab⁷⁶¹ H SO₃H H H SO₃H H CONH₂ 3-Methoxy 3 3 3 3 1ab⁷⁶² H H SO₃H SO₃H H H propyl 1ab⁷⁶³ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁶⁴ OMe H SO₃H SO₃H H OMe 1ab⁷⁶⁵ H SO₃H H H SO₃H H CONH₂ 2-Hydroxy ethyl 3 3 3 3 1ab⁷⁶⁶ H H SO₃H SO₃H H H 1ab⁷⁶⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁶⁸ OMe H SO₃H SO₃H H OMe 1ab⁷⁶⁹ H SO₃H H H SO₃H H CONH₂ 2-Fluoro ethyl 3 3 3 3 1ab⁷⁷⁰ H H SO₃H SO₃H H H 1ab⁷⁷¹ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁷² OMe H SO₃H SO₃H H OMe 1ab⁷⁷³ H SO₃H H H SO₃H H CONH₂ 2-Chloro ethyl 3 3 3 3 1ab⁷⁷⁴ H H SO₃H SO₃H H H 1ab⁷⁷⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁷⁶ OMe H SO₃H SO₃H H OMe 1ab⁷⁷⁷ H SO₃H H H SO₃H H CONH₂ 3-Chloro propyl 3 3 3 3 1ab⁷⁷⁸ H H SO₃H SO₃H H H 1ab⁷⁷⁹ Methyl H SO₃H SO₃H H Methyl 1ab⁷⁸⁰ OMe H SO₃H SO₃H H OMe 1ab⁷⁸¹ H SO₃H H H SO₃H H CONH₂ 2-(2-Hydroxy- 3 3 3 3 1ab⁷⁸² H H SO₃H SO₃H H H ethyl sulfanyl)- 1ab⁷⁸³ Methyl H SO₃H SO₃H H Methyl ethyl 1ab⁷⁸⁴ OMe H SO₃H SO₃H H OMe 1ab⁷⁸⁵ H SO₃H H H SO₃H H CONH₂ 2-(2-tert-Butyl 3 3 3 3 1ab⁷⁸⁶ H H SO₃H SO₃H H H sulfanyl-ethane 1ab⁷⁸⁷ Methyl H SO₃H SO₃H H Methyl sulfonyl)-ethyl 1ab⁷⁸⁸ OMe H SO₃H SO₃H H OMe 1ab⁷⁸⁹ H SO₃H H H SO₃H H CONH₂ 3-(4-Hydroxy 3 3 3 3 1ab⁷⁹⁰ H H SO₃H SO₃H H H butoxy) 1ab⁷⁹¹ Methyl H SO₃H SO₃H H Methyl propyl 1ab⁷⁹² OMe H SO₃H SO₃H H OMe 1ab⁷⁹³ H SO3H H H SO3H H CONH₂ 2-(2-Hydroxy 3 3 3 3 1ab⁷⁹⁴ H H SO3H SO3H H H ethoxy)ethyl 1ab⁷⁹⁵ Methyl H SO3H SO3H H Methyl 1ab⁷⁹⁶ OMe H SO3H SO3H H OMe 1ab⁷⁹⁷ H SO₃H H H SO₃H H CONH₂ 4-(2-Hydroxy- 3 3 3 3 1ab⁷⁹⁸ H H SO₃H SO₃H H H ethane 1ab⁷⁹⁹ Methyl H SO₃H SO₃H H Methyl sulfonyl)-phenyl 1ab⁸⁰⁰ OMe H SO₃H SO₃H H OMe 1ab⁸⁰¹ H SO₃H H H SO₃H H CONH₂ 3-(2-Phenoxy- 3 3 3 3 1ab⁸⁰² H H SO₃H SO₃H H H ethoxy)-propyl 1ab⁸⁰³ Methyl H SO₃H SO₃H H Methyl 1ab⁸⁰⁴ OMe H SO₃H SO₃H H OMe 1ab⁸⁰⁵ H SO₃H H H SO₃H H CONH₂ 3-Isopropoxy- 3 3 3 3 1ab⁸⁰⁶ H H SO₃H SO₃H H H propyl 1ab⁸⁰⁷ Methyl H SO₃H SO₃H H Methyl 1ab⁸⁰⁸ OMe H SO₃H SO₃H H OMe 1ab⁸⁰⁹ H SO₃H H H SO₃H H CONH₂ 3-Ethoxy-propyl 3 3 3 3 1ab⁸¹⁰ H H SO₃H SO₃H H H 1ab⁸¹¹ Methyl H SO₃H SO₃H H Methyl 1ab⁸¹² OMe H SO₃H SO₃H H OMe 1ab⁸¹³ H SO₃H H H SO₃H H CONH₂ 3-Ethoxybutyl 3 3 3 3 1ab⁸¹⁴ H H SO₃H SO₃H H H 1ab⁸¹⁵ Methyl H SO₃H SO₃H H Methyl 1ab⁸¹⁶ OMe H SO₃H SO₃H H OMe

The present invention is also directed to a process for the preparation of the dyes of formula (1) and mixtures thereof, comprising

-   a) diazotization of a compound of formula (2)

-   -   wherein R¹ to R⁸ are defined as above,

-   b) reacting the corresponding diazonium salt obtained in step a)     with the compounds of formula (3), (4), (5) and (6)

wherein R⁹ to R²⁶ are as defined above.

The diazotization of the compound of formula (2) can be performed by means of diazotization methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can advantageously be used.

The coupling reaction of the diazonium salt obtained by diazotization of the compound of the formula (2) onto the compounds of formulae (3), (4), (5) and (6) can be performed by known methods.

The compounds of the formula (2) are known and commercially available or can be synthesised by means of common chemical reactions known to a person skilled in the art such as the methods disclosed in U.S. Pat. No. 5,728,874 or DE 172 106.

The pyridines of formula (3), (4), (5) and (6) in which R⁹ and R¹⁸ represent cyano are commercially available or can be synthesized via methods disclosed in the literature such as in DE 22 30 392. Through analogy, all the diamino pyridines that are used in this invention can be synthesized as described. The obtained pyridines can be further derivatized by reactions known to persons skilled in the art, such as hydrolysis to form pyridines in which R⁹ and R¹⁸ represent carbonamide or by hydrolysis and further esterification to form pyridines in which R⁹ and R¹⁸ are alkoxycarbonyl.

The above-mentioned derivatization reactions can be carried out in alkaline or acidic media, preferably in acidic media using strong inorganic acids such as sulfuric acid or hydrochloric acid gaseous or solution, acidic resins or chlorotrimethylsilane or other suitable acid catalyst in the presence of the corresponding alcohol. The reactions are advantageously carried out under inert atmosphere at temperatures in the range from 40 to 150° C.

Alternatively, the above-mentioned derivatization reactions could be undertaken as a final step after the synthesis of the corresponding dyes with pyridone nitriles.

The dyes of the present invention can be used alone or as a mixture with other dyes according to the present invention and/or other substances.

Thus a chemical composition comprising one or more dye(s) as described above is also an aspect of the present invention.

A chemical composition consisting of two or more dyes as described above forms another preferred aspect of the present invention.

Also an aqueous solution for dying comprising one or more dye(s) as described above forms an aspect of the present invention.

The dyes of the present invention are suitable for dyeing and printing of natural, manufactured regenerated, modified or synthetic hydroxyl- amino-, and/or carboxamido-containing fiber materials and their blends by the application methods numerously described in the art for acid dyes.

Therefore the present invention also is directed to a process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with a dye as described above.

The use of a dye as described above, a chemical composition as described above or of an aqueous solution as described above for dying fibers, as well as blends of such fibres selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers forms another aspect of the present invention.

Still another aspect of the present invention is/are: Fiber and blends containing such fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers comprising one or more dye(s) of the present invention either in chemically and/or physically bound form.

The above-mentioned substrates to be dyed can be present in various forms such as but not limited to yarn, woven fabric, loop-formingly knitted fabric or carpet. For instance in the form of sheetlike structures, such as paper and leather, in the form of films, such as nylon films, or in the form of a bulk mass, for example composed of polyamide and polyurethane, in particular in the form of fibers, for example cellulose fibers. The fibers are preferably textile fibers, for example in the form of woven fabrics or yarns or in the form of hanks or wound packages.

The dyes of the present invention and their salts and/or mixtures can be used as a single dyeing colorant in dyeing or printing processes or can be part of a di-, tri- or multi-component combination colorant in dyeing or in printing compositions. The di-, tri- or multi-component shade dyeings show similar fastness level as compared to dyeing performed with a single colorant component.

Dyes of the present invention and their salts or mixtures are highly compatible with other known and/or commercially available acid dyes and they can be used together with such dyes of related chromophores and similar technical performance to obtain specific hues. Similar technical performance includes: comparable build-up, comparable fastness properties and comparable exhaustion rates during dyeings.

The dyes according to the invention can be applied to the materials mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes. This applies to both, dyeing and printing processes.

It applies in particular to the production of dyeings on fiber materials composed of wool or other natural polyamides or of synthetic polyamides and their mixtures with other fiber material. In general, the material to be dyed is introduced into the bath at a temperature of about 40° C., agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98° C. However, the dyeings can also be carried out at the boil or in a sealed dyeing apparatus at temperatures of up to 106° C.

Since the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.

The dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing. For this the dyes of the present invention need to be formulated in aqueous inks.

An Ink for digital textile printing, comprising a dye of the present invention is another aspect of the present invention.

The inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 to 50° A) by weight, more preferably from 0.5 to 30% by weight and most preferably from 1 to 15% by weight, based on the total weight of the ink.

If desired the inks may contain further dyes used in digital printing in addition to the one or more dyes of the present invention.

For the inks of the present invention to be used in the continuous flow process, a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include for example lithium nitrate and potassium nitrate. The inks of the present invention may include organic solvents at a total level of 1 to 50% by weight and preferably 5 to 30% by weight. Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1,2-ethanediol, 1,2,3-propanetriol, butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 2,3-propanediol, pentanediol, 1,4-pentanediol, 1,5-pentanediol, hexanediol, D,L-1,2-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,2-octanediol, polyalkylene glycols, for example: polyethylene glycol, polypropylene glycol, alkylene glycols having 1 to 8 alkylene groups, for example: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, low alkyl ethers of polyhydric alcohols, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether, polyalkylene glycol ethers, such as for example: polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines, such as for example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-acetylethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives, such as for example: urea, thiourea, N-methylurea, N,N′-epsilon dimethylurea, ethyleneurea, 1,1,3,3-tetramethylurea, amides, such as for example: dimethylformamide, dimethylacetamide, acetamide, ketones or keto alcohols, such as for example: acetone, diacetone alcohol, cyclic ethers, such as for example: tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma butyrolactone, epsilon-caprolactam, further sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide, N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, 1-(3-hydroxypropyl)-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolinone, 1,3-bismethoxymethylimidazolidine, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol, pyridine, piperidine, butyrolactone, trimethylpropane, 1,2-dimethoxypropane, dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether, 1,2-dimethoxypropane and trimethylpropane.

The inks of the present invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in a temperature range from 20 to 50° C. Preferred inks have a viscosity of 1.5 to 20 mPas and particularly preferred inks have a viscosity of 1.5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example: polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.

As further additives the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mN/m, which are adapted if necessary as a function of the process used (thermal or piezo technology). Useful surface-active substances include for example: all surfactants, preferably nonionic surfactants, butyldiglycol, 1,2-hexanediol.

The inks of the present invention may further comprise customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1% by weight based on the total weight of the ink.

The inks may be prepared in a conventional manner by mixing the components in water.

The inks of the invention are particularly useful in inkjet printing processes for printing a wide variety of pretreated materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and cellulosic fiber materials of any kind. Blend fabrics, for example blends of cotton, silk, wool with polyester fibers or polyamide fibers can similarly be printed.

In contrast to conventional textile printing, where the printing ink already contains all necessary chemicals, in digital or inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step.

The pretreatment of the textile substrate, for example cellulose and regenerated cellulose fibers and also silk and wool, is effected with an aqueous alkaline liquor prior to printing. In addition there is a need for thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannans.

These pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried.

The examples below serve to illustrate the invention. Parts and percentages are by weigh unless noted otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the liter.

EXAMPLE 1

8.62 g of 4,4′-diamino-biphenyl-2,2′-disulfonic acid were first dissolved in water at slightly acidic pH to give a complete solution. Ice was added to the solution and when temperature reaches 10 to 15° C., 10.6 ml of 5 N sodium nitrite solution were added dropwise into the 4,4′-diamino-biphenyl-2,2′-disulfonic acid solution. The reaction mixture was further cooled down to 0 to 8° C. using ice-salt-water bath. When temperature reached 0 to 8° C., the mixture was added dropwise into 12.38 g of concentrated HCl with 12 g of ice. Yellow suspension was formed and reaction mixture was completed within an hour.

13.21 g of a mixture of 2-amino-6-[3-(4-hydroxy-butoxy)-propylamino]-4-methyl-nicotinonitrile, 6-amino-2-[3-(4-hydroxy-butoxy)-propylamino]-4-methyl-nicotinonitrile, 2-amino-6-[2-(2-hydroxy-ethoxy)-ethylamino]-4-methyl-nicotinonitrile and 6-amino-2-[2-(2-hydroxy-ethoxy)-ethylamino]-4-methyl-nicotinonitrile were stirred in acidic water and added dropwise into the diazonium salt solution and stirred. Brilliant yellow precipitate was observed upon addition. Precipitate obtained was filtered off with suction and washed with brine giving an yellow product consisting of a mixture of the dyes 1aa¹⁵⁴, 1ab¹⁵⁴, 1aa² and 1ab². The analytic data are consistent with the assigned structure for the obtained products. The obtained products dye the targeted fibre materials in brilliant yellow shades.

Through analogy, all the dyes of formulae (1aa¹-1aa⁸¹⁶) and (1ab¹-1ab⁸¹⁶) and mixtures thereof can be synthesized according to the method described above.

Dyeing Example 1

1 part of the above-mentioned yellow product was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5 using acetic acid (80%). The dyebath was heated to 50° C. for 10 minutes and than entered with 100 parts of a woven polyamide-6 fabric. The temperature was raised to 98° C. over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60° C. and removal of the dyed material. The polyamide-6 fabric was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained give yellow shades and have very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 2

1 part of the above-mentioned yellow product was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5.5 using acetic acid (80%). The dyebath was heated to 50° C. for 10 minutes and then entered with 100 parts of a woven polyamide-6,6 fabric. The temperature was raised to 120° C. over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60° C. and removal of the dyed material. The polyamide-6,6 fabric was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained give yellow shades and have very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 3

100 parts of polyamide-6 material were padded with a 1000 parts 50° C. liquor solution that consists of 40 parts of the above-mentioned yellow product, 100 parts of urea, 20 parts of a non-ionic solubilizer based on butyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 parts of levelling assistant (based on ethoxylated aminopropyl fatty acid amide) and 810 parts of water. The material was rolled up and placed into a steaming chamber at 85 to 98° C. for 3 to 6 hours. After fixation, the fabric was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained give yellow shades and have very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 4

1 part of the above-mentioned yellow product was dissolved in 2000 parts of water and 5 parts of sodium sulphate, and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate were added. The pH was then adjusted to 4.5 using acetic acid (80%). The dyebath was heated to 50° C. for 10 minutes and then entered with 100 parts of a woven wool fabric. The temperature was raised to 100° C. over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 90° C. and removal of the dyed material. The wool fabric was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained give yellow shades and have very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 5

1 part of the above-mentioned yellow product was dissolved in 1000 parts of soft water and 7.5 parts of sodium sulphate, and 1 parts of a wetting agent (anionic) were added. 100 part of bleached cotton knitted fabric was added to this solution. The dye bath was then heated up to 98° C. with a gradient of 2° C./min then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling down to 80° C. At 80° C. the dyeing was continued for another 20 minutes. The dyed material was then removed and was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained give yellow shades and have very good light and wet fastness and also good levelness in the fibre.

Dyeing Example 6

3 parts of the above-mentioned yellow product were dissolved in 82 parts of deionized water was added into the dyebath with 15 parts of diethylene glycol at 60° C. On cooling, a yellow printing ink was obtained. The yellow printing ink can be used for ink jet printing on paper, polyamide or wool textiles.

Dyeing Example 7

4 parts of chemically bleached (pine wood) sulphite pulp were mixed up with 100 parts of 55° C. water. 1 part of the above-mentioned yellow product was dissolved in 100 parts of hot water. 80 parts of this solution were given to the mixed-up pulp and mixed for 2 minutes. After that the mixture was sized with resin size in a conventional manner and mixed for another 2 minutes. 55 parts of this solution were then diluted with 2000 parts of cold water and the paper was produced out of this solution. The yellow paper produced from the mixture has good wet fastnesses. 

The invention claimed is:
 1. A dye of formula (1)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M whereby at least two of them are SO₃M, R⁹ and R¹⁸ independent of each other is cyano, carbamoyl, substituted carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen, R¹⁰ and R¹⁹ independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl-amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio or arylthio, or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido, R¹¹, R¹², R²⁰ and R²¹ independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkyl-aminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo-alkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono-aryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamo-yl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamo-yl and SO₃M, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M, R¹³, R¹⁴, R¹⁵, R¹⁶, R²², R²³, R²⁴ and R²⁵ independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo-alkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono-aryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamo-yl and SO₃M, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M, R¹⁷ and R²⁶ independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl amino; N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythio-carbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO₃M, M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation, n, o and p independent of each other is integer 1, 2, 3 or 4, when n is 2, 3 or 4, R¹³ contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R¹⁴ independently from R¹³, when m is 2, 3 or 4, R¹⁵ contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R¹⁶ independently from R¹⁵, when o is 2, 3 or 4, R²² contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R²³ independently from R²² and when p is 2, 3 or 4, R²⁴ contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R²⁵ independently from R²⁴, the dyes of formula (1) have two to six sulfonic acid groups and whereby the bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R¹¹ and R¹², and R¹³ to R¹⁷, respectively can be positioned ortho or para to R⁹, meaning that when the amino rest bearing the substituents R¹¹ and R¹² is positioned ortho to R⁹, the amino rest bearing the substituents R¹³ to R¹⁷ is positioned para to R⁹, and vice versa; and the same applies to the amino rests bearing the substituents R²⁰ and R²¹, and R²² to R²⁶, respectively that can be positioned ortho or para to R¹⁸, meaning that when the amino rest bearing the substituents R²⁰ and R²¹ is positioned ortho to R¹⁸, the amino rest bearing the substituents R²² to R²⁶ is positioned para to R¹⁸, and vice versa.
 2. The dye according to claim 1, having formula (1a)

wherein R^(1a), R^(2a), R^(3a), R^(4a), R^(5a), R^(6a), R^(7a) and R^(8a) independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(9a) and R^(18a) independent of each other is cyano, carbamoyl or alkoxycarbonyl, R^(10a) and R^(19a) independent of each other is unsubstituted, linear or branched (C₁-C₄)-alkyl, unsubstituted (C₅-C₇)-cycloalkyl, substituted (C₅-C₇)-cycloalkyl with one or more substituents, R^(11a), R^(12a), R^(20a) and R^(21a) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkyl-thioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl-ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, R^(13a), R^(14a), R^(15a), R^(16a), R^(22a), R^(23a), R^(24a) and R^(25a) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl-ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, R^(17a) and R^(26a) independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl-ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation, m, n, o and p independent of each other is integer and is 1, 2, 3 or 4, and when n is 2, 3 or 4, R^(13a) contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R^(14a) independently from R^(13a), when m is 2, 3 or 4, R^(15a) contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R^(16a) independently from R^(15a), when o is 2, 3 or 4, R^(22a) contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R^(23a) independently from R^(22a) and when p is 2, 3 or 4, R^(24a) contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R^(25a) independently from R^(24a).
 3. A process for the production of the dye according to claim 1 and mixtures thereof, comprising a) diazotization of a compound of formula (2)

wherein R¹ to R⁸ are defined as in claim 1, b) reacting the corresponding diazonium salt obtained in step a) with the compounds of formula (3), (4), (5) and (6)

wherein R⁹ to R²⁶ are defined as in claim
 1. 4. A chemical composition comprising one or more dye(s) according to claim
 1. 5. A chemical composition consisting essentially of two or more dyes according to claim
 1. 6. An aqueous solution for dying comprising one or more chemical compounds according to claim
 1. 7. A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with the dye according to claim
 1. 8. An ink for digital textile printing, comprising a dye according to claim
 1. 9. A process for dying fibers which comprises contacting the fiber with the dye according to claim 1, wherein the fiber is selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibers, seed fibers, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibers, sisal, henequen, banana; stalk fibers, bamboo; fibers from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fiber, fur, leather materials; manufactured, regenerated and recycled fibers, cellulosic fibers; paper fibers, cellulosic regenerated fibers, viscose rayon fibers, acetate and triacetate fibers and Lyocell fibers.
 10. A fiber and blends containing a fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibers, seed fibers, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibers, sisal, henequen, banana; stalk fibers, bamboo; fibers from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fiber, fur, leather materials; manufactured, regenerated and recycled fibers, cellulosic fibers; paper fibers, cellulosic regenerated fibers, viscose rayon fibers, acetate and triacetate fibers, and Lyocell fibers comprising one or more dye(s) according to claim 1 either in chemically and/or physically bound form on the fiber.
 11. A dye of formula (1aa)

wherein R^(1aa), R^(2aa), R^(3aa), R^(4aa), R^(5aa), R^(6aa), R^(7aa) and R^(8aa) independent of each other is SO₃M, hydrogen, alkyl or alkoxy whereby at least two of them are SO₃M, R^(9aa) and R^(18aa) independent of each other is cyano or carbamoyl, R^(10aa) and R^(19aa) is methyl, m, n, o and p independent of each other is an integer and is 2, 3 or 4, R^(13aa), R^(14aa), R^(15aa), R^(16aa), R^(17aa), R^(22aa), R^(23aa), R^(24aa), R^(25aa) and R^(26aa) is hydrogen, R^(11aa), R^(20aa), R^(12aa) and R^(21aa) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclo-hexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylproyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-methoxyethyl, 3-methoxypropyl, 2-hydroxyethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 2-(2-hydroxyethylsulfanyl)-ethyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(ethyl-sulfonyl)ethanol, 3-(4-hydroxybutoxy)propyl, 2-(2-hydroxyethoxy)ethyl, 4-(2-hydroxyethane-sulfonyl)phenyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, and M is hydrogen, sodium, potassium, lithium or ammonium.
 12. The dye according to claim 11, wherein R^(11aa), R^(13aa), R^(14aa), R^(15aa), R^(16aa), R^(17aa), R^(20aa), R^(22aa), R^(23aa), R^(24aa), R^(25aa) and R^(26aa) are hydrogen.
 13. A chemical composition comprising one or more dye(s) according to claim
 11. 14. A chemical composition consisting essentially of two or more dyes according to claim
 11. 15. An aqueous solution for dying comprising one or more chemical compounds according to claim
 11. 16. A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with the dye according to claim
 11. 17. An ink for digital textile printing comprising the dye according to claim
 11. 18. A dye of formula (1ab)

wherein R^(1ab), R^(2ab), R^(3ab), R^(4ab), R^(5ab), R^(6ab), R^(7ab) and R^(8ab) independent of each other is SO₃M, hydrogen, alkyl or alkoxy whereby at least two of them are SO₃M, R^(9ab) and R^(18ab) independent of each other is cyano or carbamoyl, R^(10ab) and R^(19ab) is methyl, n, o and p independent of each other is an integer and is 2, 3 or 4, R^(13ab), R^(14ab), R^(15ab), R^(16ab), R^(17ab), R^(22ab), R^(23ab), R^(24ab), R^(25ab) and R^(26ab) is hydrogen, R^(11ab), R^(20ab), R^(12ab) and R^(21ab) independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclo-hexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylproyl, 1,2-di-methylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-methoxyethyl, 3-methoxypropyl, 2-hydroxyethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 6-hydroxy-1-[2-(2-hydroxyethylsulfanyl)-ethyl], 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(ethylsulfonyl)ethanol, 2-hydroxyethoxypropyl, 2-hydroxyethoxyethyl, 2-(ethyl sulfonyl) ethanol, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, and M is hydrogen, sodium, potassium, lithium or ammonium.
 19. A chemical composition comprising one or more dye(s) according to claim
 18. 20. The dye according to claim 18, wherein R^(11ab), R^(13ab), R^(14ab), R^(15ab), R^(16ab), R^(17ab), R^(20ab), R^(22ab), R^(23ab), R^(24ab), R^(25ab) and R^(26ab) are hydrogen.
 21. An aqueous solution for dying comprising one or more chemical compounds according to claim
 18. 22. An ink for digital textile printing comprising the dye according to claim
 18. 